Thermoplastic polycarbonate compositions with improved chemical and scratch resistance

ABSTRACT

Disclosed is a thermoplastic composition comprising a polycarbonate terpolymer comprising structures derived from structures (I), (TI) and (III), wherein (I) is a dihydroxy compound having the structure (A): 
     
       
         
         
             
             
         
       
     
     wherein n is 0 to 4 and R f  is independently a halogen atom, a C 1-10  hydrocarbon group, or a C 1-10  halogen substituted hydrocarbon group; (II) comprises a second dihydroxy compound derived from Formula (A) and different from (I) and wherein n and R f  are as previously defined; and (III) a third dihydroxy compound not derived from Formula (A), wherein the sum of the mol percent of all of structures (I) and (II) is greater than 45% relative to the sum of the molar amounts of all of structures (I), (II) and (III) in the polycarbonate terpolymer and wherein said polycarbonate terpolymer is amorphous; an impact modifier; and an ungrafted rigid copolymer. The thermoplastic composition has improved chemical resistance and scratch resistance.

BACKGROUND OF THE INVENTION

This invention is directed to thermoplastic compositions comprising anaromatic polycarbonate copolymer, and in particular thermoplasticpolycarbonate compositions having improved chemical and scratchresistance.

Thermoplastics having good chemical and/or scratch resistance are usefulin the manufacture of articles and components for a wide range ofapplications, from automobile components, to decorative articles, tohousings for electronic appliances, such as computers and cell phones.Dihydroxy aromatic compounds are generally known to be useful in thepreparation of polycarbonates that exhibit good chemical and scratchresistance and good barrier properties. Excellent mechanical propertiesare also desired in a thermoplastic composition for use in theseapplications.

There accordingly remains a need in the art for thermoplasticpolycarbonate compositions having improved chemical and scratchresistance. Desirable features of such materials also include bothexcellent mechanical properties and ease of manufacture. The mechanicalproperties of the thermoplastic composition with improved chemical andscratch resistance are desirably comparable to those of otherthermoplastic polycarbonate compositions.

SUMMARY OF THE INVENTION

The above needs are met by a thermoplastic composition comprising apolycarbonate terpolymer comprising structures derived from at leastthree different dihydroxy groups, an impact modifier and an ungraftedrigid copolymer. The ungrafted rigid copolymer optionally comprisesacrylonitrile monomer or (meth)acrylate monomer. The polycarbonateterpolymer comprises structures derived from structures (I), (II) and(III), wherein (I) is a dihydroxy compound having the structure (A):

wherein n is 0 to 4 and R^(f) is independently a halogen atom, a C₁₋₁₀hydrocarbon group, or a C₁₋₁₀ halogen substituted hydrocarbon group;(II) comprises a second dihydroxy compound derived from Formula (A) anddifferent from (I) and wherein n and R^(f) are as previously defined;and (III) a third dihydroxy compound not derived from Formula (A),wherein the sum of the mol percent of all of structures (I) and (II) isgreater than 45% relative to the sum of the molar amounts of all ofstructures (I), (II) and (III) in the polycarbonate terpolymer, andwherein said polycarbonate terpolymer is amorphous.

In another embodiment, an article comprises the above-describedthermoplastic composition.

In another embodiment, a thermoplastic composition comprises apolycarbonate terpolymer comprising structures derived from structures(I), (II) and (III), wherein (I) is a dihydroxy compound having thestructure (A):

wherein n is 0 to 4 and R^(f) is independently a halogen atom, a C₁₋₁₀hydrocarbon group, or a C₁₋₁₀ halogen substituted hydrocarbon group;(II) comprises a second dihydroxy compound derived from Formula (A) anddifferent from (I) and wherein n and R^(f) are as previously defined;and (III) a third dihydroxy compound not derived from Formula (A),wherein the sum of the mol percent of all of structures (I) and (II) isgreater than 45% relative to the sum of the molar amounts of all ofstructures (I), (II) and (III) in the polycarbonate terpolymer, theratio of dihydroxy groups (I):(II):(III) is approximately 1:1:1, andwherein the polycarbonate terpolymer is amorphous; an impact modifier;and an ungrafted rigid copolymer.

In another embodiment, a thermoplastic composition comprises apolycarbonate terpolymer comprising structures derived from structures(I), (II) and (III), wherein (I) is a dihydroxy compound having thestructure (A):

wherein n is 0; (II) comprises a second dihydroxy compound derived fromFormula (A) wherein n is 1 and R^(f) is C₁; (III) a third dihydroxycompound not derived from Formula (A), wherein the sum of the molpercent of all of structures (I) and (II) is greater than 45% relativeto the sum of the molar amounts of all of structures (I), (II) and (III)in the polycarbonate terpolymer, the ratio of dihydroxy groups(I):(II):(III) is approximately 1:1:1, and wherein the polycarbonateterpolymer is amorphous; an impact modifier; and an ungrafted rigidcopolymer. In some embodiments, the third dihydroxy compound isbisphenol A.

One method for forming an article comprises molding, extruding, shapingor forming the composition to form the article.

The above-described and other features are exemplified by the followingdetailed description.

DETAILED DESCRIPTION OF THE INVENTION

In an embodiment, a thermoplastic composition comprises a polycarbonateterpolymer comprising structures derived from structures (I), (II) and(III), wherein (I) is a dihydroxy compound having the structure (A):

wherein n is 0 to 4 and R^(f) is independently a halogen atom, a C₁₋₁₀hydrocarbon group, or a C₁₋₁₀ halogen substituted hydrocarbon group;(II) comprises a second dihydroxy compound derived from Formula (A) anddifferent from (I) and wherein n and R^(f) are as previously defined;and (III) a third dihydroxy compound not derived from Formula (A),wherein the sum of the mol percent of all of structures (I) and (II) isgreater than 45% relative to the sum of the molar amounts of all ofstructures (I), (II) and (III) in the polycarbonate terpolymer andwherein the polycarbonate terpolymer is amorphous; an impact modifier;and an ungrafted rigid copolymer.

In some embodiments, the thermoplastic composition comprises from about10 to about 85 wt. % of the polycarbonate terpolymer; from about 5 toabout 45 wt. % of the impact modifier; and from about 10 to about 45 wt.% of the ungrafted rigid copolymer, wherein the sum of the polycarbonateterpolymer, the impact modifier and the ungrafted rigid copolymer equals100 wt. %. In other embodiments, the ratio of dihydroxy groups(I):(II):(III) is approximately 1:1:1. In some embodiments, the firstdihydroxy (I) of Formula (A) n is 0, and optionally, the seconddihydroxy (II) of Formula (A) n is 1 and R^(f) is C₁.

In some embodiments, the impact modifier is ABS, MBS, ASA,polycarbonate-polysiloxane copolymer, or a combination of two or more ofthe foregoing impact modifiers. In some embodiments, the ungrafted rigidcopolymer foregoing comprises acrylonitrile monomer or (meth)acrylatemonomer, optionally SAN or PMMA.

In some embodiments, the thermoplastic composition further comprises aflow promoter, and the flow promoter optionally comprises a lowmolecular weight hydrocarbon resin derived from petroleum C₅ to C₉feedstock.

In another embodiment, a thermoplastic composition comprises apolycarbonate terpolymer comprising structures derived from structures(I), (II) and (III), wherein (I) is a dihydroxy compound having thestructure (A):

wherein n is 0 to 4 and R^(f) is independently a halogen atom, a C₁₋₁₀hydrocarbon group, or a C₁₋₁₀ halogen substituted hydrocarbon group;(II) comprises a second dihydroxy compound derived from Formula (A) anddifferent from (I) and wherein n and R^(f) are as previously defined;and (III) a third dihydroxy compound not derived from Formula (A),wherein the sum of the mol percent of all of structures (I) and (II) isgreater than 45% relative to the sum of the molar amounts of all ofstructures (I), (II) and (III) in the polycarbonate terpolymer, theratio of dihydroxy groups (I):(II):(III) is approximately 1:1:1, andwherein the polycarbonate terpolymer is amorphous; an impact modifier;and an ungrafted rigid copolymer.

In another embodiment, a thermoplastic composition comprises apolycarbonate terpolymer comprising structures derived from structures(I), (II) and (III), wherein (I) is a dihydroxy compound having thestructure (A):

wherein n is 0; (II) comprises a second dihydroxy compound derived fromFormula (A) wherein n is 1 and R^(f) is C₁; (III) a third dihydroxycompound not derived from Formula (A), wherein the sum of the molpercent of all of structures (I) and (II) is greater than 45% relativeto the sum of the molar amounts of all of structures (I), (II) and (III)in the polycarbonate terpolymer, the ratio of dihydroxy groups(I):(II):(III) is approximately 1:1:1, and wherein the polycarbonateterpolymer is amorphous; an impact modifier; and an ungrafted rigidcopolymer. In some embodiments, the third dihydroxy compound isbisphenol A.

As used herein, “amorphous” means having a glass-like structure with lowdegree of order and no crystallinity as determined by lack of a meltingendotherm when analyzed by differential scanning calorimetry (DSC) (suchas by ASTM D3418 or ISO 11357).

A thermoplastic (I), (II) and (III), wherein (I) is a dihydroxy compoundhaving the structure (A):

wherein n is 0 to 4 and R^(f) is independently a halogen atom, a C₁₋₁₀hydrocarbon group, or a C₁₋₁₀ halogen substituted hydrocarbon group;(II) comprises a second dihydroxy compound derived from Formula (A) anddifferent from (I) and wherein n and R^(f) are as previously defined;and (III) a third dihydroxy compound different from (I) and (II),wherein the sum of the mol percent of structures (I) and (II) is greaterthan 45% relative to the sum of the molar amounts of (I), (II) and (III)in the polycarbonate terpolymer and wherein said polycarbonateterpolymer is amorphous; an impact modifier; and an ungrafted rigidcopolymer is disclosed. The composition optionally comprises a flowpromoter.

The thermoplastic composition comprises a polycarbonate, wherein thepolycarbonate is a terpolymer comprising structures derived from atleast three different dihydroxy groups (I), (II) and (III), wherein atleast two dihydroxy groups ((I) and (II)) are comprised of structures ofFormula (A) and are different from each other, and the third dihydroxygroup (III) is different from the first two dihydroxy groups ((I) and(II)) and does not comprise a structure of Formula (A).

As used herein, the term “polycarbonate” refers to a polymer comprisingthe same or different carbonate units, or a copolymer that comprises thesame or different carbonate units, as well as one or more units otherthan carbonate (i.e. copolycarbonate); the term “aliphatic” refers to ahydrocarbon radical having a valence of at least one comprising a linearor branched array of carbon atoms which is not cyclic; “aromatic” refersto a radical having a valence of at least one comprising at least onearomatic group; “cycloaliphatic” refers to a radical having a valence ofat least one comprising an array of carbon atoms which is cyclic but notaromatic; “alkyl” refers to a straight or branched chain monovalenthydrocarbon radical; “alkylene” refers to a straight or branched chaindivalent hydrocarbon radical; “alkylidene” refers to a straight orbranched chain divalent hydrocarbon radical, with both valences on asingle common carbon atom; “alkenyl” refers to a straight or branchedchain monovalent hydrocarbon radical having at least two carbons joinedby a carbon-carbon double bond; “cycloalkyl” refers to a non-aromaticalicyclic monovalent hydrocarbon radical having at least three carbonatoms, with at least one degree of unsaturation; “cycloalkylene” refersto a non-aromatic alicyclic divalent hydrocarbon radical having at leastthree carbon atoms, with at least one degree of unsaturation; “aryl”refers to a monovalent aromatic benzene ring radical, or to anoptionally substituted benzene ring system radical system fused to atleast one optionally substituted benzene rings; “aromatic radical”refers to a radical having a valence of at least one comprising at leastone aromatic group; examples of aromatic radicals include phenyl,pyridyl, furanyl, thienyl, naphthyl, and the like; “arylene” refers to abenzene ring diradical or to a benzene ring system diradical fused to atleast one optionally substituted benzene ring; “alkylaryl” refers to analkyl group as defined above substituted onto an aryl as defined above;“arylalkyl” refers to an aryl group as defined above substituted onto analkyl as defined above; “alkoxy” refers to an alkyl group as definedabove connected through an oxygen radical to an adjoining group;“aryloxy” refers to an aryl group as defined above connected through anoxygen radical to an adjoining group; the modifier “about” used inconnection with a quantity is inclusive of the stated value and has themeaning dictated by the context (e.g., includes the degree of errorassociated with measurement of the particular quantity); “optional” or“optionally” means that the subsequently described event or circumstancemay or may not occur, or that the subsequently identified material mayor may not be present, and that the description includes instances wherethe event or circumstance occurs or where the material is present, andinstances where the event or circumstance does not occur or the materialis not present; and “direct bond”, where part of a structural variablespecification, refers to the direct joining of the substituentspreceding and succeeding the variable taken as a “direct bond”.

Compounds are described herein using standard nomenclature. For example,any position not substituted by any indicated group is understood tohave its valency filled by a bond as indicated, or a hydrogen atom. Adash (“−”) that is not between two letters or symbols is used toindicate a point of attachment for a substituent. For example, —CHO isattached through the carbon of the carbonyl (C═O) group. The singularforms “a,” “an,” and “the” include plural referents unless the contextclearly dictates otherwise. The endpoints of all ranges reciting thesame characteristic or component are independently combinable andinclusive of the recited endpoint. All references are incorporatedherein by reference. The terms “first,” “second,” and the like herein donot denote any order, quantity, or importance, but rather are used todistinguish one element from another. The modifier “about” used inconnection with a quantity is inclusive of the stated value and has themeaning dictated by the context (e.g., includes the degree of errorassociated with measurement of the particular quantity).

As used herein, the terms “polycarbonate” and “polycarbonate resin” meancompositions having repeating structural carbonate units of the formula(1):

in which at least about 60 percent of the total number of R¹ groups arearomatic organic radicals and the balance thereof are aliphatic,alicyclic, or aromatic radicals. In one embodiment, each R¹ is anaromatic organic radical, for example a radical of the formula (2):

-A¹-Y¹-A²-   (2)

wherein each of A¹ and A² is a monocyclic divalent aryl radical and Y¹is a bridging radical having one or two atoms that separate A¹ from A².In an exemplary embodiment, one atom separates A¹ from A². Illustrativenon-limiting examples of radicals of this type are —O—, —S—, —S(O)—,—S(O₂)—, —C(O)—, methylene, cyclohexyl-methylene,2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene,neopentylidene, cyclohexylidene, cyclopentadecylidene,cyclododecylidene, and adamantylidene. The bridging radical Y¹ may be ahydrocarbon group or a saturated hydrocarbon group such as methylene,cyclohexylidene, or isopropylidene.

Polycarbonates may be produced by the interfacial reaction of dihydroxycompounds having the formula HO—R¹—OH, wherein R¹ is as defined above.Dihydroxy compounds suitable in an interfacial reaction include thedihydroxy compounds of formula (A) as well as dihydroxy compounds offormula (3)

HO-A¹-Y¹-A²-OH   (3)

wherein Y¹, A¹ and A² are as described above. Also included arebisphenol compounds of general formula (4):

wherein R^(a) and R^(b) each represent a halogen atom or a monovalenthydrocarbon group and may be the same or different; p and q are eachindependently integers of 0 to 4; and Xa represents one of the groups offormula (5):

wherein R^(c) and R^(d) each independently represent a hydrogen atom ora monovalent linear or cyclic hydrocarbon group and R^(e) is a divalenthydrocarbon group.

Some illustrative, non-limiting examples of suitable dihydroxy compoundsinclude the following: resorcinol, 4-bromoresorcinol, hydroquinone,4,4′-dihydroxybiphenyl, 1,6-dihydroxynaphthalene,2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane,bis(4-hydroxyphenyl)diphenylmethane,bis(4-hydroxyphenyl)-1-naphthylmethane, 1,2-bis(4-hydroxyphenyl)ethane,1,1-bis(4-hydroxyphenyl)-1-phenylethane,2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,bis(4-hydroxyphenyl)phenylmethane,2,2-bis(4-hydroxy-3-bromophenyl)propane, 1,1-bis(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)isobutene,1,1-bis(4-hydroxyphenyl)cyclododecane,trans-2,3-bis(4-hydroxyphenyl)-2-butene,2,2-bis(4-hydroxyphenyl)adamantine, (alpha,alpha′-bis(4-hydroxyphenyl)toluene, bis(4-hydroxyphenyl)acetonitrile,2,2-bis(3-methyl-4-hydroxyphenyl)propane,2,2-bis(3-ethyl-4-hydroxyphenyl)propane,2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,2,2-bis(3-t-butyl-4-hydroxyphenyl)propane,2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,2,2-bis(3-allyl-4-hydroxyphenyl)propane,2,2-bis(3-methoxy-4-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)hexafluoropropane,1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene,4,4′-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone,1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycolbis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether,bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide,bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorine,2,7-dihydroxypyrene,6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane (“spirobiindanebisphenol”), 3,3-bis(4-hydroxyphenyl)phthalide,2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene,2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine,3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and2,7-dihydroxycarbazole, and the like, as well as combinations comprisingat least one of the foregoing dihydroxy compounds.

Specific examples of the types of bisphenol compounds that may berepresented by formula (3) include 1,1-bis(4-hydroxyphenyl) methane,1,1-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane(hereinafter “bisphenol A” or “BPA”), 2,2-bis(4-hydroxyphenyl) butane,2,2-bis(4-hydroxyphenyl) octane, 1,1-bis(4-hydroxyphenyl) propane,1,1-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-1-methylphenyl)propane, and 1,1-bis(4-hydroxy-t-butylphenyl) propane. Combinationscomprising at least one of the foregoing dihydroxy compounds may also beused.

The polycarbonate copolymers comprise structures derived from at leastthree different dihydroxy groups wherein at least two dihydroxy groups((I) and (II)) are comprised of structures of formula (A) and aredifferent from each other:

wherein each R^(f) is independently a halogen atom, a C₁₋₁₀ hydrocarbongroup, or a C₁₋₁₀ halogen substituted hydrocarbon group, and n is 0 to4, and the third dihydroxy group (III) is different from the first twodihydroxy groups ((I) and (II)) and does not comprise a structure ofFormula (A). For example, in one embodiment the polycarbonate copolymercomprises two structures derived from formula (A): (I) wherein n is 0(hydroquinone), and (II) wherein n is 1 and R^(f) is C₁(methylhydroquinone), and a third structure (III) that is different from(I) and (II), such as a dihydroxy group of formula 3 (such as bisphenolA). In one embodiment, the ratio of dihydroxy groups (I):(II):(III) isapproximately 1:1:1 (about 33.3% of (I), about 33.3% of (II) and about33.3% of (III)). In other embodiments, the ratio of dihydroxy groups(I):(II):(III) may be 0.05 to 0.90:0.05 to 0.90:0.05 to 0.55, optionally0.10 to 0.80:0.10 to 0.80:0.10 to 0.55, optionally 0.15 to 0.70:0.15 to0.70:0.15 to 0.55, optionally 0.20 to 0.60:0.20 to 0.60:0.20 to 0.55,optionally 0.25 to 0.50:0.25 to 0.50:0.25 to 0.50, wherein the sum ofdihydroxy groups (I) and (II) is at least 45 mol %, optionally at least50 mol %, optionally at least 60 mol %, and the polycarbonate terpolymeris amorphous.

The polycarbonate copolymer may comprise more than one of each ofstructures (I), (II) and (III). For example, the polycarbonate copolymermay comprise three structures derived from formula (A) that are alldifferent, such as hydroquinone, methylhydroquinone, and resorcinol, anda third structure (III) that is not derived from Formula A, such asbisphenol A. Additional numbers of monomers are also possible, such as 4different structures derived from Formula (A) that are different, 5different structures derived from Formula A, and the like. The sum ofthe dihydroxy groups of all structures (I) and (II) derived from FormulaA is at least 50 mol %.

Other non-limiting examples of monomer combinations for thepolycarbonate copolymers include: hydroquinone (HQ)/methyl hydroquinone(MeHQ or other substituted hydroquinones)/biphenol; HQ/MeHQ/dimethylbisphenol cyclohexane (DMBPC);HQ/MeHQ/2-phenyl-3,3-bis-(4-hydroxyphenyl) phthalimidine (PPPBP);HQ/MeHQ/1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPI);HQ/resorcinol/2,2-bis(4-hydroxyphenyl) propane (bisphenol A or BPA);HQ/chlorohydroquinone/BPA; HQ/trimethyl hydroquinone/BPA; HQ/t-butylhydroquinone/BPA, as well as other combinations of these monomers orother substituted hydroquinones or resorcinol compounds. Thepolycarbonate copolymers may be made by methods known in the art, suchas by the method described in U.S. Application Publication 2003/0149223.

Branched polycarbonates are also useful, as well as blends of a linearpolycarbonate and a branched polycarbonate. The branched polycarbonatesmay be prepared by adding a branching agent during polymerization. Thesebranching agents include polyfunctional organic compounds containing atleast three functional groups selected from hydroxyl, carboxyl,carboxylic anhydride, haloformyl, and mixtures of the foregoingfunctional groups. Specific examples include trimellitic acid,trimellitic anhydride, trimellitic trichloride, tris-p-hydroxy phenylethane, isatin-bis-phenol, tris-phenol TC(1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA(4(4(1,1-bis(p-hydroxyphenyl)-ethyl) alpha, alpha-dimethylbenzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, andbenzophenone tetracarboxylic acid. The branching agents may be added ata level of about 0.05 wt. % to about 2.0 wt. %. All types ofpolycarbonate end groups are contemplated as being useful in thepolycarbonate composition, provided that such end groups do notsignificantly affect desired properties of the thermoplasticcompositions.

“Polycarbonates” and “polycarbonate resins” as used herein furtherincludes blends of polycarbonates with other copolymers comprisingcarbonate chain units. A specific suitable copolymer is a polyestercarbonate, also known as a copolyester-polycarbonate. Such copolymersfurther contain, in addition to recurring carbonate chain units of theformula (1), repeating units of formula (6)

wherein D is a divalent radical derived from a dihydroxy compound, andmay be, for example, a C₂₋₁₀ alkylene radical, a C₆₋₂₀ alicyclicradical, a C₆₋₂₀ aromatic radical or a polyoxyalkylene radical in whichthe alkylene groups contain 2 to about 6 carbon atoms, specifically 2,3, or 4 carbon atoms; and T is a divalent radical derived from adicarboxylic acid, and may be, for example, a C₂₋₁₀ alkylene radical, aC₆₋₂₀ alicyclic radical, a C₆₋₂₀ alkyl aromatic radical, or a C₆₋₂₀aromatic radical.

In one embodiment, D is a C₂₋₆ alkylene radical. In another embodiment,D is derived from an aromatic dihydroxy compound of formula (7):

wherein each Rk is independently a halogen atom, a C₁₋₁₀ hydrocarbongroup, or a C₁₋₁₀ halogen substituted hydrocarbon group, and n is 0 to4. The halogen is usually bromine. Examples of compounds that may berepresented by the formula (7) include resorcinol, substitutedresorcinol compounds such as 5-methyl resorcinol, 5-ethyl resorcinol,5-propyl resorcinol, 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenylresorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluoro resorcinol,2,4,5,6-tetrabromo resorcinol, or the like; catechol; hydroquinone;substituted hydroquinones such as 2-methyl hydroquinone, 2-ethylhydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butylhydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone,2,3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone,2,3,5,6-tetrafluoro hydroquinone, 2,3,5,6-tetrabromo hydroquinone, orthe like; or combinations comprising at least one of the foregoingcompounds.

Examples of aromatic dicarboxylic acids that may be used to prepare thepolyesters include isophthalic or terephthalic acid,1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether,4,4′-bisbenzoic acid, and mixtures comprising at least one of theforegoing acids. Acids containing fused rings can also be present, suchas in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Specificdicarboxylic acids are terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexane dicarboxylic acid, or mixtures thereof. Aspecific dicarboxylic acid comprises a mixture of isophthalic acid andterephthalic acid wherein the weight ratio of terephthalic acid toisophthalic acid is about 10:1 to about 0.2:9.8. In another specificembodiment, D is a C₂₋₆ alkylene radical and T is p-phenylene,m-phenylene, naphthalene, a divalent cycloaliphatic radical, or amixture thereof This class of polyester includes the poly(alkyleneterephthalates).

In one specific embodiment, the polycarbonate is a linear homopolymerderived from bisphenol A, in which each of A¹ and A² is p-phenylene andY¹ is isopropylidene.

Suitable polycarbonates can be manufactured by processes such asinterfacial polymerization and melt polymerization. Although thereaction conditions for interfacial polymerization may vary, anexemplary process generally involves dissolving or dispersing a dihydricphenol reactant in aqueous caustic soda or potash, adding the resultingmixture to a suitable water-immiscible solvent medium, and contactingthe reactants with a carbonate precursor in the presence of a suitablecatalyst such as triethylamine or a phase transfer catalyst, undercontrolled pH conditions, e.g., about 8 to about 10. The most commonlyused water immiscible solvents include methylene chloride,1,2-dichloroethane, chlorobenzene, toluene, and the like. Suitablecarbonate precursors include, for example, a carbonyl halide such ascarbonyl bromide or carbonyl chloride, or a haloformate such as abishaloformate of a dihydric phenol (e.g., the bischloroformates ofbisphenol A, hydroquinone, or the like) or a glycol (e.g., thebishaloformate of ethylene glycol, neopentyl glycol, polyethyleneglycol, or the like). Combinations comprising at least one of theforegoing types of carbonate precursors may also be used.

Among the phase transfer catalysts that may be used are catalysts of theformula (R³)₄Q X, wherein each R³ is the same or different, and is aC₁₋₁₀ alkyl group; Q is a nitrogen or phosphorus atom; and X is ahalogen atom or a C₁₋₁₈ alkoxy group or C₆₋₁₈₈ aryloxy group. Suitablephase transfer catalysts include, for example, [CH₃(CH₂)₃]₄NX,[CH₃(CH₂)₃]₄PX, [CH₃(CH₂)₅]₄NX, [CH₃(CH₂)₆]₄NX, [CH₃(CH₂)₄]₄NX,CH₃[CH₃(CH₂)₃]₃NX, and CH₃[CH₃(CH₂)₂]₃NX, wherein X is Cl⁻, Br⁻, a C₁₋₈alkoxy group or a C₆₋₁₈ aryloxy group. An effective amount of a phasetransfer catalyst may be about 0.1 to about 10 wt. % based on the weightof bisphenol in the phosgenation mixture. In another embodiment aneffective amount of phase transfer catalyst may be about 0.5 to about 2wt. % based on the weight of bisphenol in the phosgenation mixture.

Alternatively, melt processes may be used to make the polycarbonates.Generally, in the melt polymerization process, polycarbonates may beprepared by co-reacting, in a molten state, the dihydroxy reactant(s)and a diaryl carbonate ester, such as diphenyl carbonate, in thepresence of a transesterification catalyst in a Banbury® mixer, twinscrew extruder, or the like to form a uniform dispersion. Volatilemonohydric phenol is removed from the molten reactants by distillationand the polymer is isolated as a molten residue.

The polycarbonate resins may also be prepared by interfacialpolymerization. Rather than utilizing the dicarboxylic acid per se, itis possible, and sometimes even preferred, to employ the reactivederivatives of the acid, such as the corresponding acid halides, inparticular the acid dichlorides and the acid dibromides. Thus, forexample, instead of using isophthalic acid, terephthalic acid, ormixtures thereof, it is possible to employ isophthaloyl dichloride,terephthaloyl dichloride, and mixtures thereof.

In addition to the polycarbonates described above, it is also possibleto use combinations of the polycarbonate with other thermoplasticpolymers, for example combinations of polycarbonates and/orpolycarbonate copolymers with polyesters. As used herein, a“combination” is inclusive of all mixtures, blends, alloys, and thelike. Suitable polyesters comprise repeating units of formula (6), andmay be, for example, poly(alkylene dicarboxylates), liquid crystallinepolyesters, and polyester copolymers. It is also possible to use abranched polyester in which a branching agent, for example, a glycolhaving three or more hydroxyl groups or a trifunctional ormultifunctional carboxylic acid has been incorporated. Furthermore, itis sometime desirable to have various concentrations of acid andhydroxyl end groups on the polyester, depending on the ultimate end useof the composition.

In one embodiment, poly(alkylene terephthalates) are used. Specificexamples of suitable poly(alkylene terephthalates) are poly(ethyleneterephthalate) (PET), poly(1,4-butylene terephthalate) (PBT),poly(ethylene naphthanoate) (PEN), poly(butylene naphthanoate), (PBN),(polypropylene terephthalate) (PPT), polycyclohexanedimethanolterephthalate (PCT), and combinations comprising at least one of theforegoing polyesters. Also contemplated are the above polyesters with aminor amount, e.g., from about 0.5 to about 10 percent by weight, ofunits derived from an aliphatic diacid and/or an aliphatic polyol tomake copolyesters.

Blends and/or mixtures of more than one polycarbonate may also be used.For example, a high flow and a low flow polycarbonate may be blendedtogether.

The thermoplastic composition further includes one or more impactmodifier compositions to increase the impact resistance of thethermoplastic composition. These impact modifiers may include anelastomer-modified graft copolymer comprising (i) an elastomeric (i.e.,rubbery) polymer substrate having a Tg less than about 10° C., morespecifically less than about −10° C., or more specifically about −40° C.to −80° C., and (ii) a rigid polymeric superstrate grafted to theelastomeric polymer substrate. As is known, elastomer-modified graftcopolymers may be prepared by first providing the elastomeric polymer,then polymerizing the constituent monomer(s) of the rigid phase in thepresence of the elastomer to obtain the graft copolymer. The grafts maybe attached as graft branches or as shells to an elastomer core. Theshell may merely physically encapsulate the core, or the shell may bepartially or essentially completely grafted to the core.

Suitable materials for use as the elastomer phase include, for example,conjugated diene rubbers; copolymers of a conjugated diene with lessthan about 50 wt. % of a copolymerizable monomer; olefin rubbers such asethylene propylene copolymers (EPR) or ethylene-propylene-diene monomerrubbers (EPDM); ethylene-vinyl acetate rubbers; silicone rubbers;elastomeric C₁₋₈ alkyl (meth)acrylates; elastomeric copolymers of C₁₋₈alkyl (meth)acrylates with butadiene and/or styrene; or combinationscomprising at least one of the foregoing elastomers. As used herein, theterminology “(meth)acrylate monomers” refers collectively to acrylatemonomers and methacrylate monomers.

Suitable conjugated diene monomers for preparing the elastomer phase areof formula (8):

wherein each X^(b) is independently hydrogen, C₁-C₅ alkyl, or the like.Examples of conjugated diene monomers that may be used are butadiene,isoprene, 1,3-heptadiene, methyl-1,3-pentadiene,2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-pentadiene; 1,3- and2,4-hexadienes, and the like, as well as mixtures comprising at leastone of the foregoing conjugated diene monomers. Specific conjugateddiene homopolymers include polybutadiene and polyisoprene.

Copolymers of a conjugated diene rubber may also be used, for examplethose produced by aqueous radical emulsion polymerization of aconjugated diene and one or more monomers copolymerizable therewith.Monomers that are suitable for copolymerization with the conjugateddiene include monovinylaromatic monomers containing condensed aromaticring structures, such as vinyl naphthalene, vinyl anthracene and thelike, or monomers of formula (9):

wherein each X^(c) is independently hydrogen, C₁-C₁₂ alkyl, C₃-C₁₂cycloalkyl, C₆-C₁₂ aryl, C₇-C₁₂ aralkyl, C₇-C₁₂ alkaryl, C₁-C₁₂ alkoxy,C₃-C₁₂ cycloalkoxy, C₆-C₁₂ aryloxy, chloro, bromo, or hydroxy, and R ishydrogen, C₁-C₅ alkyl, bromo, or chloro. Examples of suitablemonovinylaromatic monomers that may be used include styrene,3-methylstyrene, 3,5-diethylstyrene, 4-n-propylstyrene,alpha-methylstyrene, alpha-methyl vinyltoluene, alpha-chlorostyrene,alpha-bromostyrene, dichlorostyrene, dibromostyrene,tetra-chlorostyrene, and the like, and combinations comprising at leastone of the foregoing compounds. Styrene and/or alpha-methylstyrene maybe used as monomers copolymerizable with the conjugated diene monomer.

Other monomers that may be copolymerized with the conjugated diene aremonovinylic monomers such as itaconic acid, acrylamide, N-substitutedacrylamide or methacrylamide, maleic anhydride, maleimide, N-alkyl-,aryl-, or haloaryl-substituted maleimide, glycidyl (meth)acrylates, andmonomers of the generic formula (10):

wherein R is hydrogen, C₁-C₅ alkyl, bromo, or chloro, and X^(d) iscyano, C₁-C₁₂ alkoxycarbonyl, C₁-C₁₂ aryloxycarbonyl, hydroxy carbonyl,or the like. Examples of monomers of formula (10) include acrylonitrile,ethacrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile,beta-chloroacrylonitrile, alpha-bromoacrylonitrile, acrylic acid, methyl(meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl(meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,2-ethylhexyl (meth)acrylate, and the like, and combinations comprisingat least one of the foregoing monomers. Monomers such as n-butylacrylate, ethyl acrylate, and 2-ethylhexyl acrylate are commonly used asmonomers copolymerizable with the conjugated diene monomer. Mixtures ofthe foregoing monovinyl monomers and monovinylaromatic monomers may alsobe used.

Suitable (meth)acrylate monomers suitable for use as the elastomericphase may be cross-linked, particulate emulsion homopolymers orcopolymers of C₁₋₈ alkyl (meth)acrylates, in particular C₄₋₆ alkylacrylates, for example n-butyl acrylate, t-butyl acrylate, n-propylacrylate, isopropyl acrylate, 2-ethylhexyl acrylate, and the like, andcombinations comprising at least one of the foregoing monomers. The C₁₋₈alkyl (meth)acrylate monomers may optionally be polymerized in admixturewith up to 15 wt. % of comonomers of formulas (8), (9), or (10).Exemplary comonomers include but are not limited to butadiene, isoprene,styrene, methyl methacrylate, phenyl methacrylate, penethylmethacrylate,N-cyclohexylacrylamide, vinyl methyl ether or acrylonitrile, andmixtures comprising at least one of the foregoing comonomers.Optionally, up to 5 wt. % a polyfunctional crosslinking comonomer may bepresent, for example divinylbenzene, alkylenediol di(meth)acrylates suchas glycol bisacrylate, alkylenetriol tri(meth)acrylates, polyesterdi(meth)acrylates, bisacrylamides, triallyl cyanurate, triallylisocyanurate, allyl (meth)acrylate, diallyl maleate, diallyl fumarate,diallyl adipate, triallyl esters of citric acid, triallyl esters ofphosphoric acid, and the like, as well as combinations comprising atleast one of the foregoing crosslinking agents.

The elastomer phase may be polymerized by mass, emulsion, suspension,solution or combined processes such as bulk-suspension, emulsion-bulk,bulk-solution or other techniques, using continuous, semibatch, or batchprocesses. The particle size of the elastomer substrate is not critical.For example, an average particle size of about 0.001 to about 25micrometers, specifically about 0.01 to about 15 micrometers, or evenmore specifically about 0. 1 to about 8 micrometers may be used foremulsion based polymerized rubber lattices. A particle size of about 0.5to about 10 micrometers, specifically about 0.6 to about 1.5 micrometersmay be used for bulk polymerized rubber substrates. Particle size may bemeasured by simple light transmission methods or capillary hydrodynamicchromatography (CHDF). The elastomer phase may be a particulate,moderately cross-linked conjugated butadiene or C₄₋₆ alkyl acrylaterubber, and preferably has a gel content greater than 70%. Also suitableare mixtures of butadiene with styrene and/or C₄₋₆ alkyl acrylaterubbers.

The elastomeric phase may provide about 5 wt. % to about 95 wt. % of thetotal graft copolymer, more specifically about 20 wt. % to about 90 wt.%, and even more specifically about 40 wt. % to about 85 wt. % of theelastomer-modified graft copolymer, the remainder being the rigid graftphase.

The rigid phase of the elastomer-modified graft copolymer may be formedby graft polymerization of a mixture comprising a monovinylaromaticmonomer and optionally one or more comonomers in the presence of one ormore elastomeric polymer substrates. The above-describedmonovinylaromatic monomers of formula (9) may be used in the rigid graftphase, including styrene, alpha-methyl styrene, halostyrenes such asdibromostyrene, vinyltoluene, vinylxylene, butylstyrene,para-hydroxystyrene, methoxystyrene, or the like, or combinationscomprising at least one of the foregoing monovinylaromatic monomers.Suitable comonomers include, for example, the above-describedmonovinylic monomers and/or monomers of the general formula (10). In oneembodiment, R is hydrogen or C₁-C₂ alkyl, and X^(d) is cyano or C₁-C₁₂alkoxycarbonyl. Specific examples of suitable comonomers for use in therigid phase include acrylonitrile, ethacrylonitrile, methacrylonitrile,methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate,isopropyl (meth)acrylate, and the like, and combinations comprising atleast one of the foregoing comonomers.

The relative ratio of monovinylaromatic monomer and comonomer in therigid graft phase may vary widely depending on the type of elastomersubstrate, type of monovinylaromatic monomer(s), type of comonomer(s),and the desired properties of the impact modifier. The rigid phase maygenerally comprise up to 100 wt. % of monovinyl aromatic monomer,specifically about 30 to about 100 wt. %, more specifically about 50 toabout 90 wt. % monovinylaromatic monomer, with the balance beingcomonomer(s).

Depending on the amount of elastomer-modified polymer present, aseparate matrix or continuous phase of ungrafted rigid polymer orcopolymer may be simultaneously obtained along with theelastomer-modified graft copolymer. Typically, such impact modifierscomprise about 40 wt. % to about 95 wt. % elastomer-modified graftcopolymer and about 5 wt. % to about 65 wt. % graft (co)polymer, basedon the total weight of the impact modifier. In another embodiment, suchimpact modifiers comprise about 50 wt. % to about 85 wt. %, morespecifically about 75 wt. % to about 85 wt. % rubber-modified graftcopolymer, together with about 15 wt. % to about 50 wt. %, morespecifically about 15 wt. % to about 25 wt. % graft (co)polymer, basedon the total weight of the impact modifier.

Another specific type of elastomer-modified impact modifier comprisesstructural units derived from at least one silicone rubber monomer, abranched acrylate rubber monomer having the formulaH₂C═C(R^(g))C(O)OCH₂CH₂R^(h), wherein R^(g) is hydrogen or a C₁-C₈linear or branched hydrocarbyl group and R^(h) is a branched C₃-C₁₆hydrocarbyl group; a first graft link monomer; a polymerizablealkenyl-containing organic material; and a second graft link monomer.The silicone rubber monomer may comprise, for example, a cyclicsiloxane, tetraalkoxysilane, trialkoxysilane, (acryloxy)alkoxysilane,(mercaptoalkyl)alkoxysilane, vinylalkoxysilane, or allylalkoxysilane,alone or in combination, e.g., decamethylcyclopentasiloxane,dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane,tetramethyltetraphenylcyclotetrasiloxane,tetramethyltetravinylcyclotetrasiloxane, octaphenylcyclotetrasiloxane,octamethylcyclotetrasiloxane and/or tetraethoxysilane.

Exemplary branched acrylate rubber monomers include iso-octyl acrylate,6-methyloctyl acrylate, 7-methyloctyl acrylate, 6-methylheptyl acrylate,and the like, alone or in combination. The polymerizablealkenyl-containing organic material may be, for example, a monomer offormula (9) or (10), e.g., styrene, alpha-methylstyrene, acrylonitrile,methacrylonitrile, or an unbranched (meth)acrylate such as methylmethacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethylacrylate, n-propyl acrylate, or the like, alone or in combination.

The at least one first graft link monomer may be an(acryloxy)alkoxysilane, a (mercaptoalkyl)alkoxysilane, avinylalkoxysilane, or an allylalkoxysilane, alone or in combination,e.g., (gamma-methacryloxypropyl)(dimethoxy)methylsilane and/or(3-mercaptopropyl)trimethoxysilane. The at least one second graft linkmonomer is a polyethylenically unsaturated compound having at least oneallyl group, such as allyl methacrylate, triallyl cyanurate, or triallylisocyanurate, alone or in combination.

The silicone-acrylate impact modifier compositions can be prepared byemulsion polymerization, wherein, for example at least one siliconerubber monomer is reacted with at least one first graft link monomer ata temperature from about 30° C. to about 110° C. to form a siliconerubber latex, in the presence of a surfactant such asdodecylbenzenesulfonic acid. Alternatively, a cyclic siloxane such ascyclooctamethyltetrasiloxane and a tetraethoxyorthosilicate may bereacted with a first graft link monomer such as(gamma-methacryloxypropyl)methyldimethoxysilane, to afford siliconerubber having an average particle size from about 100 nanometers toabout 2 micrometers. At least one branched acrylate rubber monomer isthen polymerized with the silicone rubber particles, optionally in thepresence of a cross linking monomer, such as allylmethacrylate in thepresence of a free radical generating polymerization catalyst such asbenzoyl peroxide. This latex is then reacted with a polymerizablealkenyl-containing organic material and a second graft link monomer. Thelatex particles of the graft silicone-acrylate rubber hybrid may beseparated from the aqueous phase through coagulation (by treatment witha coagulant) and dried to a fine powder to produce the silicone-acrylaterubber impact modifier composition. This method can be generally usedfor producing the silicone-acrylate impact modifier having a particlesize from about 100 nanometers to about two micrometers.

Processes known for the formation of the foregoing elastomer-modifiedgraft copolymers include mass, emulsion, suspension, and solutionprocesses, or combined processes such as bulk-suspension, emulsion-bulk,bulk-solution or other techniques, using continuous, semibatch, or batchprocesses.

If desired, the foregoing types of impact modifiers may be prepared byan emulsion polymerization process that is free of basic materials suchas alkali metal salts of C₆₋₃₀ fatty acids, for example sodium stearate,lithium stearate, sodium oleate, potassium oleate, and the like, alkalimetal carbonates, amines such as dodecyl dimethyl amine, dodecyl amine,and the like, and ammonium salts of amines, or any other material, suchas an acid, that contains a degradation catalyst. Such materials arecommonly used as surfactants in emulsion polymerization, and maycatalyze transesterification and/or degradation of polycarbonates.Instead, ionic sulfate, sulfonate or phosphate surfactants may be usedin preparing the impact modifiers, particularly the elastomericsubstrate portion of the impact modifiers. Suitable surfactants include,for example, C₁₋₂₂ alkyl or C₇₋₂₅ alkylaryl sulfonates, C₁₋₂₂ alkyl orC₇₋₂₅ alkylaryl C₁₋₂₂ alkyl or C₇₋₂₅ alkylaryl phosphates, substitutedsilicates, and mixtures thereof A specific surfactant is a C₆₋₁₆,specifically a C₈₋₁₂ alkyl sulfonate. This emulsion polymerizationprocess is described and disclosed in various patents and literature ofsuch companies as Rohm & Haas and General Electric Company. In thepractice, any of the above-described impact modifiers may be usedproviding it is free of the alkali metal salts of fatty acids, alkalimetal carbonates and other basic materials.

A specific impact modifier of this type is a methylmethacrylate-butadiene-styrene (MBS) impact modifier wherein thebutadiene substrate is prepared using above-described sulfonates,sulfates, or phosphates as surfactants. Other examples ofelastomer-modified graft copolymers besides ABS and MBS include but arenot limited to acrylonitrile-styrene-butyl acrylate (ASA), methylmethacrylate-acrylonitrile-butadiene-styrene (MABS), andacrylonitrile-ethylene-propylene-diene-styrene (AES).

In some embodiments, the impact modifier is a graft polymer having ahigh rubber content, i.e., greater than or equal to about 50 wt. %,optionally greater than or equal to about 60 wt. % by weight of thegraft polymer. The rubber is preferably present in an amount less thanor equal to about 95 wt. %, optionally less than or equal to about 90wt. % of the graft polymer.

The rubber forms the backbone of the graft polymer, and is preferably apolymer of a conjugated diene having the formula (11):

wherein X^(e) is hydrogen, C₁-C₅ alkyl, chlorine, or bromine. Examplesof dienes that may be used are butadiene, isoprene, 1,3-hepta-diene,methyl-1,3-pentadiene, 2,3-dimethyl-1,3-butadiene,2-ethyl-1,3-pentadiene; 1,3- and 2,4-hexadienes, chloro and bromosubstituted butadienes such as dichlorobutadiene, bromobutadiene,dibromobutadiene, mixtures comprising at least one of the foregoingdienes, and the like. A preferred conjugated diene is butadiene.Copolymers of conjugated dienes with other monomers may also be used,for example copolymers of butadiene-styrene, butadiene-acrylonitrile,and the like. Alternatively, the backbone may be an acrylate rubber,such as one based on n-butyl acrylate, ethylacrylate,2-ethylhexylacrylate, mixtures comprising at least one of the foregoing,and the like. Additionally, minor amounts of a diene may becopolymerized in the acrylate rubber backbone to yield improvedgrafting.

After formation of the backbone polymer, a grafting monomer ispolymerized in the presence of the backbone polymer. One preferred typeof grafting monomer is a monovinylaromatic hydrocarbon having theformula (12):

wherein X^(b) is as defined above and X^(f) is hydrogen, C₁-C₁₀ alkyl,C₁-C₁₀ cycloalkyl, C₁-C₁₀ alkoxy, C₆-C₁₈ alkyl, C₆-C₁₈ aralkyl, C₆-C₁₈aryloxy, chlorine, bromine, and the like. Examples include styrene,3-methylstyrene, 3,5-diethylstyrene, 4-n-propylstyrene,alpha-methylstyrene, alpha-methyl vinyltoluene, alpha-chlorostyrene,alpha-bromostyrene, dichlorostyrene, dibromostyrene,tetra-chlorostyrene, mixtures comprising at least one of the foregoingcompounds, and the like.

A second type of grafting monomer that may be polymerized in thepresence of the polymer backbone are acrylic monomers of formula (13):

wherein X^(b) is as previously defined and Y² is cyano, C₁-C₁₂alkoxycarbonyl, or the like. Examples of such acrylic monomers includeacrylonitrile, ethacrylonitrile, methacrylonitrile,alpha-chloroacrylonitrile, beta-chloroacrylonitrile,alpha-bromoacrylonitrile, beta-bromoacrylonitrile, methyl acrylate,methyl methacrylate, ethyl acrylate, butyl acrylate, propyl acrylate,isopropyl acrylate, mixtures comprising at least one of the foregoingmonomers, and the like.

A mixture of grafting monomers may also be used, to provide a graftcopolymer. An example of a suitable mixture comprises amonovinylaromatic hydrocarbon and an acrylic monomer. Examples of graftcopolymers suitable for use include, but are not limited to,acrylonitrile-butadiene-styrene (ABS) andmethacrylonitrile-butadiene-styrene (MBS) resins. Suitable high-rubberacrylonitrile-butadiene-styrene resins are available from GeneralElectric Company as BLENDEX® grades 131, 336, 338, 360, and 415.

The composition may optionally comprise a polycarbonate-polysiloxanecopolymer comprising polycarbonate blocks and polydiorganosiloxaneblocks. The polycarbonate blocks in the copolymer comprise repeatingstructural units of formula (1) as described above, for example whereinR¹ is of formula (2) as described above. These units may be derived fromreaction of dihydroxy compounds of formula (3) as described above. Inone embodiment, the dihydroxy compound is bisphenol A, in which each ofA¹ and A² is p-phenylene and Y¹ is isopropylidene.

The polydiorganosiloxane blocks comprise repeating structural units offormula (14) (sometimes referred to herein as ‘siloxane’):

wherein each occurrence of R is same or different, and is a C₁₋₁₃monovalent organic radical. For example, R may be a C₁-C₁₃ alkyl group,C₁-C₁₃ alkoxy group, C₂-C₁₃ alkenyl group, C₂-C₁₃ alkenyloxy group,C₃-C₆ cycloalkyl group, C₃-C₆ cycloalkoxy group, C₆-C₁₀ aryl group,C₆-C₁₀ aryloxy group, C₇-C₁₃ aralkyl group, C₇-C₁₃ aralkoxy group,C₇-C₁₃ alkaryl group, or C₇-C₁₃ alkaryloxy group. Combinations of theforegoing R groups may be used in the same copolymer.

The value of D in formula (14) may vary widely depending on the type andrelative amount of each component in the thermoplastic composition, thedesired properties of the composition, and like considerations.Generally, D may have an average value of 2 to about 1000, specificallyabout 2 to about 500, more specifically about 5 to about 100. In oneembodiment, D has an average value of about 10 to about 75, and in stillanother embodiment, D has an average value of about 40 to about 60.Where D is of a lower value, e.g., less than about 40, it may bedesirable to use a relatively larger amount of thepolycarbonate-polysiloxane copolymer. Conversely, where D is of a highervalue, e.g., greater than about 40, it may be necessary to use arelatively lower amount of the polycarbonate-polysiloxane copolymer.

A combination of a first and a second (or more)polycarbonate-polysiloxane copolymers may be used, wherein the averagevalue of D of the first copolymer is less than the average value of D ofthe second copolymer.

In one embodiment, the polydiorganosiloxane blocks are provided byrepeating structural units of formula (15):

wherein D is as defined above; each R may be the same or different, andis as defined above; and Ar may be the same or different, and is asubstituted or unsubstituted C₆-C₃₀ arylene radical, wherein the bondsare directly connected to an aromatic moiety. Suitable Ar groups informula (15) may be derived from a C₆-C₃₀ dihydroxyarylene compound, forexample a dihydroxyarylene compound of formula (3), (4), or (7) above.Combinations comprising at least one of the foregoing dihydroxyarylenecompounds may also be used. Specific examples of suitabledihydroxyarlyene compounds are 1,1-bis(4-hydroxyphenyl) methane,1,1-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane,2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane,1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl) n-butane,2,2-bis(4-hydroxy-1-methylphenyl) propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl sulphide), and1,1-bis(4-hydroxy-t-butylphenyl) propane. Combinations comprising atleast one of the foregoing dihydroxy compounds may also be used.

Such units may be derived from the corresponding dihydroxy compound ofthe following formula (16):

wherein Ar and D are as described above. Such compounds are furtherdescribed in U.S. Pat. No. 4,746,701 to Kress et al. Compounds of thisformula may be obtained by the reaction of a dihydroxyarylene compoundwith, for example, an alpha, omega-bisacetoxypolydiorangonosiloxaneunder phase transfer conditions.

In another embodiment the polydiorganosiloxane blocks comprise repeatingstructural units of formula (17):

wherein R and D are as defined above. R² in formula (17) is a divalentC₂-C₈ aliphatic group. Each M in formula (19) may be the same ordifferent, and may be a halogen, cyano, nitro, C₁-C₈ alkylthio, C₁-C₈alkyl, C₁-C₈ alkoxy, C₂-C₈ alkenyl, C₂-C₈ alkenyloxy group, C₃-C₈cycloalkyl, C₃-C₈ cycloalkoxy, C₆-C₁₀ aryl, C₆-C₁₀ aryloxy, C₇-C₁₂aralkyl, C₇-C₁₂ aralkoxy, C₇-C₁₂ alkaryl, or C₇-C₁₂ alkaryloxy, whereineach n is independently 0, 1, 2, 3, or 4.

In one embodiment, M is bromo or chloro, an alkyl group such as methyl,ethyl, or propyl, an alkoxy group such as methoxy, ethoxy, or propoxy,or an aryl group such as phenyl, chlorophenyl, or tolyl; R² is adimethylene, trimethylene or tetramethylene group; and R is a C₁₋₁₈alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such asphenyl, chlorophenyl or tolyl. In another embodiment, R is methyl, or amixture of methyl and trifluoropropyl, or a mixture of methyl andphenyl. In still another embodiment, M is methoxy, n is one, R² is adivalent C₁-C₃ aliphatic group, and R is methyl.

These units may be derived from the corresponding dihydroxypolydiorganosiloxane (18):

wherein R, D, M, R², and n are as described above.

Such dihydroxy polysiloxanes can be made by effecting a platinumcatalyzed addition between a siloxane hydride of the formula (19),

wherein R and D are as previously defined, and an aliphaticallyunsaturated monohydric phenol. Suitable aliphatically unsaturatedmonohydric phenols included, for example, eugenol, 2-alkylphenol,4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol,4-allyl-2-t-butoxyphenol, 4-phenyl-2-phenylphenol,2-methyl-4-propylphenol, 2-allyl-4,6-dimethylphenol,2-allyl-4-bromo-6-methylphenol, 2-allyl-6-methoxy-4-methylphenol and2-allyl-4,6-dimethylphenol. Mixtures comprising at least one of theforegoing may also be used.

The polycarbonate-polysiloxane copolymer may be manufactured by reactionof diphenolic polysiloxane (18) with a carbonate source and a dihydroxyaromatic compound of formula (3), optionally in the presence of a phasetransfer catalyst as described above. Suitable conditions are similar tothose useful in forming polycarbonates. For example, the copolymers areprepared by phosgenation, at temperatures from below 0° C. to about 100°C., preferably about 25° C. to about 50° C. Since the reaction isexothermic, the rate of phosgene addition may be used to control thereaction temperature. The amount of phosgene required will generallydepend upon the amount of the dihydric reactants. Alternatively, thepolycarbonate-polysiloxane copolymers may be prepared by co-reacting ina molten state, the dihydroxy monomers and a diaryl carbonate ester,such as diphenyl carbonate, in the presence of a transesterificationcatalyst as described above.

In the production of the polycarbonate-polysiloxane copolymer, theamount of dihydroxy polydiorganosiloxane is selected so as to providethe desired amount of polydiorganosiloxane units in the copolymer. Theamount of polydiorganosiloxane units may vary widely, i.e., may be about1 wt. % to about 99 wt. % of polydimethylsiloxane, or an equivalentmolar amount of another polydiorganosiloxane, with the balance beingcarbonate units. The particular amounts used will therefore bedetermined depending on desired physical properties of the thermoplasticcomposition, the value of D (within the range of 2 to about 1000), andthe type and relative amount of each component in the thermoplasticcomposition, including the type and amount of polycarbonate, type andamount of impact modifier, type and amount of polycarbonate-polysiloxanecopolymer, and type and amount of any other additives. Suitable amountsof dihydroxy polydiorganosiloxane can be determined by one of ordinaryskill in the art without undue experimentation using the guidelinestaught herein. For example, the amount of dihydroxy polydiorganosiloxanemay be selected so as to produce a copolymer comprising about 1 wt. % toabout 75 wt. %, or about 1 wt. % to about 50 wt. % polydimethylsiloxane,or an equivalent molar amount of another polydiorganosiloxane. In oneembodiment, the copolymer comprises about 5 wt. % to about 40 wt. %,optionally about 5 wt. % to about 25 wt. % polydimethylsiloxane, or anequivalent molar amount of another polydiorganosiloxane, with thebalance being polycarbonate. In a particular embodiment, the copolymermay comprise about 20 wt. % siloxane.

The composition further comprises an ungrafted rigid copolymer. In oneembodiment, the ungrafted rigid copolymer comprises acrylonitrilemonomer. The rigid copolymer is additional to any rigid copolymerpresent in the impact modifier. It may be the same as any of the rigidcopolymers described above, without the elastomer modification. Therigid copolymers generally have a Tg greater than about 15° C.,specifically greater than about 20° C., and include, for example,polymers derived from monovinylaromatic monomers containing condensedaromatic ring structures, such as vinyl naphthalene, vinyl anthraceneand the like, or monomers of formula (9) as broadly described above, forexample styrene and alpha-methyl styrene; monovinylic monomers such asitaconic acid, acrylamide, N-substituted acrylamide or methacrylamide,maleic anhydride, maleimide, N-alkyl, aryl or haloaryl substitutedmaleimide, glycidyl (meth)acrylates, and monomers of the general formula(10) as broadly described above, for example acrylonitrile, methylacrylate and methyl methacrylate; and copolymers of the foregoing, forexample styrene-acrylonitrile (SAN), styrene-alpha-methylstyrene-acrylonitrile, methyl methacrylate-acrylonitrile-styrene, andmethyl methacrylate-styrene.

The rigid copolymer may comprise about 1 to about 99 wt. %, specificallyabout 20 to about 95 wt. %, more specifically about 40 to about 90 wt. %of vinylaromatic monomer, together with 1 to about 99 wt. %,specifically about 5 to about 80 wt. %, more specifically about 10 toabout 60 wt. % of copolymerizable monovinylic monomers. In oneembodiment the rigid copolymer is SAN, which may comprise about 50 toabout 99 wt. % styrene, with the balance acrylonitrile, specificallyabout 60 to about 90 wt. % styrene, and more specifically about 65 toabout 85 wt. % styrene, with the remainder acrylonitrile.

In another embodiment, the ungrafted rigid copolymer comprises a(meth)acrylate monomer. The rigid copolymers include, for example, apoly(alkyl (meth)acrylate), wherein the alkyl group is straight orbranched-chain, and has 1 or 2 carbons atoms. In one embodiment therigid copolymer is a poly(alkyl (meth)acrylate), specifically apoly(methyl methacrylate) (PMMA). PMMA may be produced by thepolymerization of methyl methacrylate monomer, and may be derived by (1)the reaction of acetone cyanohydrin, methanol, and sulphuric acid or (2)the oxidation of tert-butyl alcohol to methacrolein and then tomethacrylic acid followed by the esterification reaction with methanol.As is known, PMMA homopolymer is difficult to obtain, and therefore isavailable commercially and used herein as a mixture of the homopolymerand various copolymers of methyl methacrylate and C₁-C₄ alkyl acrylates,such as ethyl acrylate. “PMMA” as used herein therefore includes suchmixtures, which are commercially available from, for example, Atofinaunder the trade designations V825, V826, V920, V045, and VM, and fromLucite under the trade names CLG340, CLG356, CLG960, CLG902, CMG302.

Blends comprising more than one ungrafted rigid copolymer may also beused, if desired.

The rigid copolymer may be manufactured by bulk, suspension, or emulsionpolymerization. In one embodiment, the rigid copolymer is manufacturedby bulk polymerization using a boiling reactor. The rigid copolymer mayhave a weight average molecular weight of about 50,000 to about 300,000as measured by GPC using polystyrene standards. In one embodiment, theweight average molecular weight of the rigid copolymer is about 50,000to about 200,000.

The thermoplastic composition optionally comprises a flow promoter toimprove flow and other properties, such as a low molecular weighthydrocarbon resin. Particularly useful classes of low molecular weighthydrocarbon resins are those derived from petroleum C₅ to C₉ feedstockthat are derived from unsaturated C₅ to C₉ monomers obtained frompetroleum cracking. Non-limiting examples include olefins, e.g.pentenes, hexenes, heptenes and the like; diolefins, e.g. pentadienes,hexadienes and the like; cyclic olefins and diolefins, e.g.cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, methylcyclopentadiene and the like; cyclic diolefin dienes, e.g.,dicyclopentadiene, methylcyclopentadiene dimer and the like; andaromatic hydrocarbons, e.g. vinyltoluenes, indenes, methylindenes andthe like. The resins can additionally be partially or fullyhydrogenated.

Examples of commercially suitable low molecular weight hydrocarbonresins derived from petroleum C₅ to C₉ feedstock include the following:hydrocarbon resins available from Eastman Chemical under the trademarkPiccotac®, the aromatic hydrocarbon resins available from EastmanChemical under the trademark Picco®, the fully hydrogenated alicyclichydrocarbon resin based on C₉ monomers available from Arakawa ChemicalInc. under the trademark Arkon® and sold, depending on softening point,as Arkon® P140, P125, P115, P100, P90, P70 or the partially hydrogenatedhydrocarbon resins sold as Arkon® M135, M115, M100 and M90, the fully orpartially hydrogenated hydrocarbon resin available from Eastman Chemicalunder the tradename Regalite® and sold, depending on softening point, asRegalite® R1100, S1100, R1125, R1090 and R1010, or the partiallyhydrogenated resins sold as Regalite® R7100, R9100, S5100 and S7125, thehydrocarbon resins available from Exxon Chemical under the tradeEscorez®, sold as the Escorez® 1000, 2000 and 5000 series, based on C₅,C₉ feedstock and mixes thereof, or the hydrocarbon resins sold as theEscorez® 5300, 5400 and 5600 series based on cyclic and C₉ monomers,optionally hydrogenated and the pure aromatic monomer hydrocarbon resinssuch as for instance the styrene , α-methyl styrene based hydrocarbonresins available from Eastman Chemical under the tradename Kristalex®.Low molecular weight hydrocarbon resins are generally used in amounts ofabout 0.1 to about 10 parts by weight, based on 100 parts by weight ofthe polycarbonate terpolymer, the impact modifier and the ungraftedrigid copolymer.

The relative amount of each component of the thermoplastic compositionwill depend on the particular type of polycarbonate(s) used, thepresence of any other resins, and the particular impact modifier(s), andthe rigid graft copolymer, as well as the desired properties of thecomposition. Particular amounts may be readily selected by one ofordinary skill in the art using the guidance provided herein.

In one embodiment, the thermoplastic composition comprises about 10 toabout 75 wt. % polycarbonate terpolymer component, about 5 to about 45wt. % impact modifier, and about 10 to about 45 ungrafted rigidcopolymer, wherein the sum of the polycarbonate terpolymer, the impactmodifier composition and the ungrafted rigid copolymer equals 100 wt. %.In another embodiment, the thermoplastic composition comprises about 40to about 70 wt. % polycarbonate terpolymer, about 10 to about 30 wt. %impact modifier, and about 20 to about 40 wt. % ungrafted rigidcopolymer, wherein the sum of the polycarbonate terpolymer, the impactmodifier composition and the ungrafted rigid copolymer equals 100 wt. %.The thermoplastic composition optionally comprises a flow promoter in anamount of from about 0.1 to about 20 wt. %, based on 100 wt. % of theterpolymer, the impact modifier and the ungrafted rigid copolymer.

In addition to the polycarbonate terpolymer comprising structuresderived from at least three different dihydroxy groups, the impactmodifier and the ungrafted rigid copolymer, the thermoplasticcomposition may include various additives such as fillers, reinforcingagents, stabilizers, and the like, with the proviso that the additivesdo not adversely affect the desired properties of the thermoplasticcompositions.

Examples of suitable fillers or reinforcing agents include any materialsknown for these uses. For example, suitable fillers and reinforcingagents include silicates and silica powders such as aluminum silicate(mullite), synthetic calcium silicate, zirconium silicate, fused silica,crystalline silica graphite, natural silica sand, or the like; boronpowders such as boron-nitride powder, boron-silicate powders, or thelike; oxides such as TiO₂, aluminum oxide, magnesium oxide, or the like;calcium sulfate (as its anhydride, dihydrate or trihydrate); calciumcarbonates such as chalk, limestone, marble, synthetic precipitatedcalcium carbonates, or the like; talc, including fibrous, modular,needle shaped, lamellar talc, or the like; wollastonite; surface-treatedwollastonite; glass spheres such as hollow and solid glass spheres,silicate spheres, cenospheres, aluminosilicate (armospheres), or thelike; kaolin, including hard kaolin, soft kaolin, calcined kaolin,kaolin comprising various coatings known in the art to facilitatecompatibility with the polymeric matrix resin, or the like; singlecrystal fibers or “whiskers” such as silicon carbide, alumina, boroncarbide, iron, nickel, copper, or the like; fibers (including continuousand chopped fibers) such as asbestos, carbon fibers, glass fibers, suchas E, A, C, ECR, R, S, D, or NE glasses, or the like; sulfides such asmolybdenum sulfide, zinc sulfide or the like; barium compounds such asbarium titanate, barium ferrite, barium sulfate, heavy spar, or thelike; metals and metal oxides such as particulate or fibrous aluminum,bronze, zinc, copper and nickel or the like; flaked fillers such asglass flakes, flaked silicon carbide, aluminum diboride, aluminumflakes, steel flakes or the like; fibrous fillers, for example shortinorganic fibers such as those derived from blends comprising at leastone of aluminum silicates, aluminum oxides, magnesium oxides, andcalcium sulfate hemihydrate or the like; natural fillers andreinforcements, such as wood flour obtained by pulverizing wood, fibrousproducts such as cellulose, cotton, sisal, jute, starch, cork flour,lignin, ground nut shells, corn, rice grain husks or the like; organicfillers such as polytetrafluoroethylene; reinforcing organic fibrousfillers formed from organic polymers capable of forming fibers such aspoly(ether ketone), polyimide, polybenzoxazole, poly(phenylene sulfide),polyesters, polyethylene, aromatic polyamides, aromatic polyimides,polyetherimides, polytetrafluoroethylene, acrylic resins, poly(vinylalcohol) or the like; as well as additional fillers and reinforcingagents such as mica, clay, feldspar, flue dust, fillite, quartz,quartzite, perlite, tripoli, diatomaceous earth, carbon black, or thelike, or combinations comprising at least one of the foregoing fillersor reinforcing agents.

The fillers and reinforcing agents may be coated with a layer ofmetallic material to facilitate conductivity, or surface treated withsilanes to improve adhesion and dispersion with the polymeric matrixresin. In addition, the reinforcing fillers may be provided in the formof monofilament or multifilament fibers and may be used either alone orin combination with other types of fiber, through, for example,co-weaving or core/sheath, side-by-side, orange-type or matrix andfibril constructions, or by other methods known to one skilled in theart of fiber manufacture. Suitable cowoven structures include, forexample, glass fiber-carbon fiber, carbon fiber-aromatic polyimide(aramid) fiber, and aromatic polyimide fiberglass fiber or the like.Fibrous fillers may be supplied in the form of, for example, rovings,woven fibrous reinforcements, such as 0-90 degree fabrics or the like;non-woven fibrous reinforcements such as continuous strand mat, choppedstrand mat, tissues, papers and felts or the like; or three-dimensionalreinforcements such as braids. Fillers are generally used in amounts ofabout zero to about 50 parts by weight, optionally about 1 to about 20parts by weight, and in some embodiments, about 4 to about 15 parts byweight, based on 100 parts by weight of the polycarbonate terpolymer,the impact modifier and the ungrafted rigid copolymer.

In addition, the thermoplastic composition may include various additivesordinarily incorporated in resin compositions of this type, with theproviso that the additives are preferably selected so as to notsignificantly adversely affect the desired properties of thethermoplastic composition. Mixtures of additives may be used. Suchadditives may be mixed at a suitable time during the mixing of thecomponents for forming the composition.

The compositions described herein may comprise a primary antioxidant or“stabilizer” (e.g., a hindered phenol and/or secondary aryl amine) and,optionally, a secondary antioxidant (e.g., a phosphate and/orthioester). Suitable antioxidant additives include, for example,organophosphites such as tris(nonyl phenyl)phosphite,tris(2,4-di-t-butylphenyl)phosphite,bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite or the like; alkylated monophenols orpolyphenols; alkylated reaction products of polyphenols with dienes,such as tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane, or the like; butylated reaction products of para-cresol ordicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenylethers; alkylidene-bisphenols; benzyl compounds; esters ofbeta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydricor polyhydric alcohols; esters ofbeta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid withmonohydric or polyhydric alcohols; esters of thioalkyl or thioarylcompounds such as distearylthiopropionate, dilaurylthiopropionate,ditridecylthiodipropionate,octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionateor the like; amides ofbeta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid or the like, orcombinations comprising at least one of the foregoing antioxidants.Antioxidants are generally used in amounts of about 0.01 to about 1parts by weight, optionally about 0.05 to about 0.5 parts by weight,based on 100 parts by weight of the polycarbonate terpolymer, the impactmodifier and the ungrafted rigid copolymer.

Suitable heat stabilizer additives include, for example,organophosphites such as triphenyl phosphite,tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono-anddi-nonylphenyl)phosphite or the like; phosphonates such asdimethylbenzene phosphonate or the like, phosphates such as trimethylphosphate, or the like, or combinations comprising at least one of theforegoing heat stabilizers. Heat stabilizers are generally used inamounts of about 0.01 to about 5 parts by weight, optionally about 0.05to about 0.3 parts by weight, based on 100 parts by weight of thepolycarbonate terpolymer, the impact modifier and the ungrafted rigidcopolymer.

Light stabilizers and/or ultraviolet light (UV) absorbing additives mayalso be used. Suitable light stabilizer additives include, for example,benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole,2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and 2-hydroxy-4-n-octoxybenzophenone, or the like, or combinations comprising at least one ofthe foregoing light stabilizers. Light stabilizers are generally used inamounts of about 0.01 to about 10 parts by weight, optionally about 0.1to about 1 parts by weight, based on 100 parts by weight of thepolycarbonate terpolymer, the impact modifier and the ungrafted rigidcopolymer.

Suitable UV absorbing additives include for example,hydroxybenzophenones; hydroxybenzotriazoles; hydroxybenzotriazines;cyanoacrylates; oxanilides; benzoxazinones;2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (CYASORB™5411); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB™ 531);2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)-phenol(CYASORB™ 1164); 2,2′-(1,4- phenylene)bis(4H-3,1-benzoxazin-4-one)(CYASORB™ UV-3638);1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane(UVINUL™ 3030); 2,2′-(1,4-phenylene) bis(4H-3,1-benzoxazin-4-one);1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane;nano-size inorganic materials such as titanium oxide, cerium oxide, andzinc oxide, all with particle size less than about 100 nanometers; orthe like, or combinations comprising at least one of the foregoing UVabsorbers. UV absorbers are generally used in amounts of about 0.1 toabout 5 parts by weight, based on 100 parts by weight of thepolycarbonate terpolymer, the impact modifier and the ungrafted rigidcopolymer.

Plasticizers, lubricants, and/or mold release agents additives may alsobe used. There is considerable overlap among these types of materials,which include, for example, phthalic acid esters such asdioctyl-4,5-epoxy-hexahydrophthalate;tris-(octoxycarbonylethyl)isocyanurate; tristearin; di- orpolyfunctional aromatic phosphates such as resorcinol tetraphenyldiphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and thebis(diphenyl) phosphate of bisphenol-A; poly-alpha-olefins; epoxidizedsoybean oil; silicones, including silicone oils; esters, for example,fatty acid esters such as alkyl stearyl esters, e.g., methyl stearate;stearyl stearate, pentaerythritol tetrastearate, and the like; mixturesof methyl stearate and hydrophilic and hydrophobic nonionic surfactantscomprising polyethylene glycol polymers, polypropylene glycol polymers,and copolymers thereof, e.g., methyl stearate andpolyethylene-polypropylene glycol copolymers in a suitable solvent;waxes such as beeswax, montan wax, paraffin wax or the like. Suchmaterials are generally used in amounts of about 0.1 to about 20 partsby weight, optionally about 1 to about 10 parts by weight, based on 100parts by weight of the polycarbonate terpolymer, the impact modifier andthe ungrafted rigid copolymer.

The term “antistatic agent” refers to monomeric, oligomeric, orpolymeric materials that can be processed into polymer resins and/orsprayed onto materials or articles to improve conductive properties andoverall physical performance. Examples of monomeric antistatic agentsinclude glycerol monostearate, glycerol distearate, glyceroltristearate, ethoxylated amines, primary, secondary and tertiary amines,ethoxylated alcohols, alkyl sulfates, alkylarylsulfates,alkylphosphates, alkylaminesulfates, alkyl sulfonate salts such assodium stearyl sulfonate, sodium dodecylbenzenesulfonate or the like,quaternary ammonium salts, quaternary ammonium resins, imidazolinederivatives, sorbitan esters, ethanolamides, betaines, or the like, orcombinations comprising at least one of the foregoing monomericantistatic agents.

Exemplary polymeric antistatic agents include certain polyesteramides,polyether-polyamide (polyetheramide) block copolymers,polyetheresteramide block copolymers, polyetheresters, or polyurethanes,each containing polyalkylene glycol moieties such as polyethyleneglycol, polypropylene glycol, polytetramethylene glycol, and the like.Such polymeric antistatic agents are commercially available, such as,for example, Pelestat™ 6321 (Sanyo), Pebax™ MH1657 (Atofina), andIrgastat™ P18 and P22 (Ciba-Geigy). Other polymeric materials that maybe used as antistatic agents are inherently conducting polymers such aspolyaniline (commercially available as PANIPOL®EB from Panipol),polypyrrole and polythiophene (commercially available from Bayer), whichretain some of their intrinsic conductivity after melt processing atelevated temperatures. In one embodiment, carbon fibers, carbonnanofibers, carbon nanotubes, carbon black, or any combination of theforegoing may be used in a polymeric resin containing chemicalantistatic agents to render the composition electrostaticallydissipative. Antistatic agents are generally used in amounts of about0.1 to about 10 parts by weight, based on 100 parts by weight of thepolycarbonate terpolymer, the impact modifier and the ungrafted rigidcopolymer.

Colorants such as pigment and/or dye additives may also be present.Suitable pigments include for example, inorganic pigments such as metaloxides and mixed metal oxides such as zinc oxide, titanium dioxides,iron oxides or the like; sulfides such as zinc sulfides, or the like;aluminates; sodium sulfo-silicates sulfates, chromates, or the like;carbon blacks; zinc ferrites; ultramarine blue; Pigment Brown 24;Pigment Red 101; Pigment Yellow 119; organic pigments such as azos,di-azos, quinacridones, perylenes, naphthalene tetracarboxylic acids,flavanthrones, isoindolinones, tetrachloroisoindolinones,anthraquinones, anthanthrones, dioxazines, phthalocyanines, and azolakes; Pigment Blue 60, Pigment Red 122, Pigment Red 149, Pigment Red177, Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue15, Pigment Green 7, Pigment Yellow 147 and Pigment Yellow 150, orcombinations comprising at least one of the foregoing pigments. Pigmentsare generally used in amounts of about 0.01 to about 10 parts by weight,based on 100 parts by weight of the polycarbonate terpolymer, the impactmodifier and the ungrafted rigid copolymer.

Suitable dyes are generally organic materials and include, for example,coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile redor the like; lanthanide complexes; hydrocarbon and substitutedhydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; scintillationdyes such as oxazole or oxadiazole dyes; aryl- or heteroaryl-substitutedpoly (C₂₋₈) olefin dyes; carbocyanine dyes; indanthrone dyes;phthalocyanine dyes; oxazine dyes; carbostyryl dyes;napthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyldyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes;arylmethane dyes; azo dyes; indigoid dyes, thioindigoid dyes, diazoniumdyes; nitro dyes; quinone imine dyes; aminoketone dyes; tetrazoliumdyes; thiazole dyes; perylene dyes, perinone dyes;bis-benzoxazolylthiophene (BBOI); triarylmethane dyes; xanthene dyes;thioxanthene dyes; naphthalimide dyes; lactone dyes; fluorophores suchas anti- stokes shift dyes which absorb in the near infrared wavelengthand emit in the visible wavelength, or the like; luminescent dyes suchas 7-amino-4-methylcoumarin;3-(2′-benzothiazolyl)-7-diethylaminocoumarin;2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole;2,5-bis-(4-biphenylyl)-oxazole; 2,2′-dimethyl-p-quaterphenyl;2,2-dimethyl-p-terphenyl; 3,5,3,″″,5,″″-tetra-t-butyl-p-quinquephenyl;2,5-diphenylfuran; 2,5-diphenyloxazole; 4,4′-diphenylstilbene;4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran;1,1′-diethyl-2,2′-carbocyanine iodide;3,3′-diethyl-4,4′,5,5′-dibenzothiatricarbocyanine iodide;7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2;7-dimethylamino-4-methylquinolone-2;2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3-ethylbenzothiazoliumperchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate;2-(1-naphthyl)-5-phenyloxazole; 2,2′-p-phenylen-bis(5-phenyloxazole);rhodamine 700; rhodamine 800; pyrene; chrysene; rubrene; coronene, orthe like, or combinations comprising at least one of the foregoing dyes.Dyes are generally used in amounts of about 0.1 to about 10 ppm, basedon 100 parts by weight of the polycarbonate terpolymer, the impactmodifier and the ungrafted rigid copolymer.

Suitable flame retardants that may be added may be organic compoundsthat include phosphorus, bromine, and/or chlorine. Non-brominated andnon-chlorinated phosphorus-containing flame retardants may be preferredin certain applications for regulatory reasons, for example organicphosphates and organic compounds containing phosphorus-nitrogen bonds.

One type of exemplary organic phosphate is an aromatic phosphate of theformula (GO)₃P═O, wherein each G is independently an alkyl, cycloalkyl,aryl, alkaryl, or aralkyl group, provided that at least one G is anaromatic group. Two of the G groups may be joined together to provide acyclic group, for example, diphenyl pentaerythritol diphosphate, whichis described by Axelrod in U.S. Pat. No. 4,154,775. Other suitablearomatic phosphates may be, for example, phenyl bis(dodecyl) phosphate,phenyl bis(neopentyl) phosphate, phenyl bis(3,5,5′-trimethylhexyl)phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate,bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate,bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate,bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate, 2-chloroethyldiphenyl phosphate, p-tolyl bis(2,5,5′-trimethylhexyl) phosphate,2-ethylhexyl diphenyl phosphate, or the like. A specific aromaticphosphate is one in which each G is aromatic, for example, triphenylphosphate, tricresyl phosphate, isopropylated triphenyl phosphate, andthe like.

Di- or polyfunctional aromatic phosphorus-containing compounds are alsouseful, for example, compounds of the formulas below:

wherein each G¹ is independently a hydrocarbon having 1 to about 30carbon atoms; each G² is independently a hydrocarbon or hydrocarbonoxyhaving 1 to about 30 carbon atoms; each X^(a) is as defined above; eachX is independently a bromine or chlorine; m is 0 to 4, and n is 1 toabout 30. Examples of suitable di- or polyfunctional aromaticphosphorus-containing compounds include resorcinol tetraphenyldiphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and thebis(diphenyl) phosphate of bisphenol-A, respectively, their oligomericand polymeric counterparts, and the like.

Exemplary suitable flame retardant compounds containingphosphorus-nitrogen bonds include phosphonitrilic chloride, phosphorusester amides, phosphoric acid amides, phosphonic acid amides, phosphinicacid amides, tris(aziridinyl) phosphine oxide.

Halogenated materials may also be used as flame retardants, for examplehalogenated compounds and resins of formula (21):

wherein R is an alkylene, alkylidene or cycloaliphatic linkage, e.g.,methylene, ethylene, propylene, isopropylene, isopropylidene, butylene,isobutylene, amylene, cyclohexylene, cyclopentylidene, or the like; oran oxygen ether, carbonyl, amine, or a sulfur containing linkage, e.g.,sulfide, sulfoxide, sulfone, or the like. R can also consist of two ormore alkylene or alkylidene linkages connected by such groups asaromatic, amino, ether, carbonyl, sulfide, sulfoxide, sulfone, or thelike.

Ar and Ar′ in formula (21) are each independently mono- orpolycarbocyclic aromatic groups such as phenylene, biphenylene,terphenylene, naphthylene, or the like.

Y is an organic, inorganic, or organometallic radical, for example (1)halogen, e.g., chlorine, bromine, iodine, fluorine or (2) ether groupsof the general formula OE, wherein E is a monovalent hydrocarbon radicalsimilar to X or (3) monovalent hydrocarbon groups of the typerepresented by R or (4) other substituents, e.g., nitro, cyano, and thelike, said substituents being essentially inert provided that there isat least one and optionally two halogen atoms per aryl nucleus.

When present, each X is independently a monovalent hydrocarbon group,for example an alkyl group such as methyl, ethyl, propyl, isopropyl,butyl, decyl, or the like; an aryl groups such as phenyl, naphthyl,biphenyl, xylyl, tolyl, or the like; and aralkyl group such as benzyl,ethylphenyl, or the like; a cycloaliphatic group such as cyclopentyl,cyclohexyl, or the like. The monovalent hydrocarbon group may itselfcontain inert substituents.

Each d is independently 1 to a maximum equivalent to the number ofreplaceable hydrogens substituted on the aromatic rings comprising Ar orAr′. Each e is independently 0 to a maximum equivalent to the number ofreplaceable hydrogens on R. Each a, b, and c is independently a wholenumber, including 0. When b is not 0, neither a nor c may be 0.Otherwise either a or c, but not both, may be 0. Where b is 0, thearomatic groups are joined by a direct carbon-carbon bond.

The hydroxyl and Y substituents on the aromatic groups, Ar and Ar′ canbe varied in the ortho, meta or para positions on the aromatic rings andthe groups can be in any possible geometric relationship with respect toone another.

Included within the scope of the above formula are bisphenols of whichthe following are representative: 2,2-bis-(3,5-dichlorophenyl)-propane;bis-(2-chlorophenyl)-methane; bis(2,6-dibromophenyl)-methane;1,1-bis-(4-iodophenyl)-ethane; 1,2-bis-(2,6-dichlorophenyl)-ethane;1,1-bis-(2-chloro-4-iodophenyl)ethane;1,1-bis-(2-chloro-4-methylphenyl)-ethane;1,1-bis-(3,5-dichlorophenyl)-ethane;2,2-bis-(3-phenyl-4-bromophenyl)-ethane;2,6-bis-(4,6-dichloronaphthyl)-propane;2,2-bis-(2,6-dichlorophenyl)-pentane;2,2-bis-(3,5-dibromophenyl)-hexane; bis-(4-chlorophenyl)-phenyl-methane;bis-(3,5-dichlorophenyl)-cyclohexylmethane;bis-(3-nitro-4-bromophenyl)-methane;bis-(4-hydroxy-2,6-dichloro-3-methoxyphenyl)-methane; and2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane 2,2bis-(3-bromo-4-hydroxyphenyl)-propane. Also included within the abovestructural formula are: 1,3-dichlorobenzene, 1,4-dibromobenzene,1,3-dichloro-4-hydroxybenzene, and biphenyls such as2,2′-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene,2,4′-dibromobiphenyl, and 2,4′-dichlorobiphenyl as well as decabromodiphenyl oxide, and the like.

Also useful are oligomeric and polymeric halogenated aromatic compounds,such as a copolycarbonate of bisphenol A and tetrabromobisphenol A and acarbonate precursor, e.g., phosgene. Metal synergists, e.g., antimonyoxide, may also be used with the flame retardant.

Inorganic flame retardants may also be used, for example salts of C₂₋₁₆alkyl sulfonate salts such as potassium perfluorobutane sulfonate (Rimarsalt), potassium perfluoroctane sulfonate, tetraethylammoniumperfluorohexane sulfonate, and potassium diphenylsulfone sulfonate, andthe like; salts formed by reacting for example an alkali metal oralkaline earth metal (for example lithium, sodium, potassium, magnesium,calcium and barium salts) and an inorganic acid complex salt, forexample, an oxo-anion, such as alkali metal and alkaline-earth metalsalts of carbonic acid, such as Na₂CO₃, K₂CO₃, MgCO₃, CaCO₃, and BaCO₃or a fluoro-anion complex such as Li₃AlF₆, BaSiF₆, KBF₄, K₃AlF₆, KAlF₄,K₂SiF₆, and/or Na₃AlF₆ or the like.

Anti-drip agents may also be used, for example a fibril forming ornon-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE).The anti-drip agent may be encapsulated by a rigid copolymer asdescribed above, for example SAN. PTFE encapsulated in SAN is known asTSAN. Encapsulated fluoropolymers may be made by polymerizing theencapsulating polymer in the presence of the fluoropolymer, for example,in an aqueous dispersion. TSAN may provide significant advantages overPTFE, in that TSAN may be more readily dispersed in the composition. Asuitable TSAN may comprise, for example, about 50 wt. % PTFE and about50 wt. % SAN, based on the total weight of the encapsulatedfluoropolymer. The SAN may comprise, for example, about 75 wt. % styreneand about 25 wt. % acrylonitrile based on the total weight of thecopolymer. Alternatively, the fluoropolymer may be pre-blended in somemanner with a second polymer, such as for, example, an aromaticpolycarbonate resin or SAN to form an agglomerated material for use asan anti-drip agent. Either method may be used to produce an encapsulatedfluoropolymer.

Where a foam is desired, suitable blowing agents include, for example,low boiling halohydrocarbons and those that generate carbon dioxide;blowing agents that are solid at room temperature and when heated totemperatures higher than their decomposition temperature, generate gasessuch as nitrogen, carbon dioxide or ammonia gas, such asazodicarbonamide, metal salts of azodicarbonamide, 4,4′oxybis(benzenesulfonylhydrazide), sodium bicarbonate, ammoniumcarbonate, or the like; or combinations comprising at least one of theforegoing blowing agents.

The thermoplastic compositions may be manufactured by methods generallyavailable in the art, for example, in one embodiment, in one manner ofproceeding, the polycarbonate terpolymer, impact modifier, and aromaticvinyl copolymer and any other optional components (such as antioxidants,mold release agents, and the like) are first blended, in a Henschel™high speed mixer or other suitable mixer/blender. Other low shearprocesses including but not limited to hand mixing may also accomplishthis blending. The blend is then fed into the throat of a twin-screwextruder via a hopper. Alternatively, one or more of the components maybe incorporated into the composition by feeding directly into theextruder at the throat and/or downstream through a sidestuffer. Suchadditives may also be compounded into a masterbatch with a desiredpolymeric resin and fed into the extruder. The extruder is generallyoperated at a temperature higher than that necessary to cause thecomposition to flow. The extrudate is immediately quenched in a waterbatch and pelletized. The pellets, so prepared, when cutting theextrudate may be one-fourth inch long or less as desired. Such pelletsmay be used for subsequent molding, shaping, or forming.

Shaped, formed, or molded articles comprising the polycarbonatecompositions are also provided. The polycarbonate compositions may bemolded into useful shaped articles by a variety of means such asinjection molding, extrusion, rotational molding, blow molding andthermoforming to form articles such as, for example, computer andbusiness machine housings such as housings for monitors, handheldelectronic device housings such as housings for cell phones, electricalconnectors, and components of lighting fixtures, ornaments, homeappliances, roofs, greenhouses, sun rooms, swimming pool enclosures,electronic device casings and signs and the like. In addition, thepolycarbonate compositions may be used for such applications asautomotive panel and trim. Examples of suitable articles are exemplifiedby but are not limited to aircraft, automotive, truck, military vehicle(including automotive, aircraft, and water-borne vehicles), scooter, andmotorcycle exterior and interior components, including panels, quarterpanels, rocker panels, trim, fenders, doors, deck-lids, trunk lids,hoods, bonnets, roofs, bumpers, fascia, grilles, mirror housings, pillarappliques, cladding, body side moldings, wheel covers, hubcaps, doorhandles, spoilers, window frames, headlamp bezels, headlamps, taillamps, tail lamp housings, tail lamp bezels, license plate enclosures,roof racks, and running boards; enclosures, housings, panels, and partsfor outdoor vehicles and devices; enclosures for electrical andtelecommunication devices; outdoor furniture; aircraft components; boatsand marine equipment, including trim, enclosures, and housings; outboardmotor housings; depth finder housings; personal water-craft; jet-skis;pools; spas; hot tubs; steps; step coverings; building and constructionapplications such as glazing, roofs, windows, floors, decorative windowfurnishings or treatments; treated glass covers for pictures, paintings,posters, and like display items; wall panels, and doors; counter tops;protected graphics; outdoor and indoor signs; enclosures, housings,panels, and parts for automatic teller machines (ATM); computer;desk-top computer; portable computer; lap-top computer; hand heldcomputer housings; monitor; printer; keyboards; FAX machine; copier;telephone; phone bezels; mobile phone; radio sender; radio receiver;enclosures, housings, panels, and parts for lawn and garden tractors,lawn mowers, and tools, including lawn and garden tools; window and doortrim; sports equipment and toys; enclosures, housings, panels, and partsfor snowmobiles; recreational vehicle panels and components; playgroundequipment; shoe laces; articles made from plastic-wood combinations;golf course markers; utility pit covers; light fixtures; lightingappliances; network interface device housings; transformer housings; airconditioner housings; cladding or seating for public transportation;cladding or seating for trains, subways, or buses; meter housings;antenna housings; cladding for satellite dishes; coated helmets andpersonal protective equipment; coated synthetic or natural textiles;coated painted articles; coated dyed articles; coated fluorescentarticles; coated foam articles; and like applications. The inventionfurther contemplates additional fabrication operations on said articles,such as, but not limited to, molding, in-mold decoration, baking in apaint oven, lamination, and/or thermoforming. The articles made from thecomposition of the present invention may be used widely in automotiveindustry, home appliances, electrical components, andtelecommunications.

The compositions are further illustrated by the following non-limitingexamples, which were prepared from the components set forth in Table 1.

TABLE 1 Material Description Source PC-1 BPA polycarbonate resin made bya melt process with GE Plastics MW 22 kg/mol measured on a PC standardbasis PC-2 BPA polycarbonate resin made by a melt process with GEPlastics MW 30 kg/mol measured on a PC standard basis PC-3 BPApolycarbonate resin made by an interfacial process GE Plastics with MW35 kg/mol measured on a PC standard basis Co-PC-1 MeHQ/HQ/BPAcopolycarbonate resin (33/34/33 mol %) GE Plastics made by a meltprocess with MW 24 kg/mol measured on a PC standard basis Co-PC-2MeHQ/HQ/BPA copolycarbonate resin (33/34/33 mol %) GE Plastics made by amelt process with MW 30 kg/mol measured on a PC standard basis ABS Highrubber graft emulsion polymerized ABS comprising GE Plastics about 11.1wt. % acrylonitrile and about 38.5 wt. % styrene grafted to about 51 wt.% polybutadiene with a crosslink density of 43–55% PMMA Methylmethacrylate (MMA)-ethyl acrylate (EA) copolymer, Lucite/Atofinacomprising about 95.6 mol % MMA and about 4.4 mol % EA SAN-1 Styreneacrylonitrile comprising about 25 wt. % GE Plastics acrylonitrile and 75wt. % styrene SAN-2 Styrene acrylonitrile comprising about 27 wt. % GEPlastics acrylonitrile and 73 wt. % styrene PC-SiPolysiloxane-polycarbonate copolymer comprising units GE Plasticsderived from BPA and polysiloxane having an absolute weight averagemolecular weight of about 30000 g/mol, and a dimethylsiloxane content ofabout 20 wt. % FP Flow promoter (Low molecular weight hydrocarbon resinArakawa made from C₅–C₉ petroleum feedstock) (Arkon ® P125) ChemicalInc. PETS Pentaerythritol tetrastearate Faci AO-1 Primary antioxidant(Irganox ™ 1076) Ciba AO-2 Secondary antioxidant (Irgafos ™ 168) CibaPigment Pigment Black 7 Cabot/Degussa

Each of the sample compositions was prepared according to formulationsin Table 2. All amounts are in weight percent unless otherwise noted.Samples C1 to C4 are control samples using conventional BPApolycarbonate resin, ABS and SAN; and samples C5 to C8 are controlsamples using conventional BPA polycarbonate resin, ABS and PMMA insteadof SAN. Samples Ex.1 to Ex.8 are examples of the invention withdifferent amounts of the polycarbonate terpolymer, impact modifier andungrafted rigid copolymer. In each of the examples, samples wereprepared by melt extrusion on a Werner & Pfleiderer™ 25 mm co-rotatingtwin screw extruder at a nominal barrel temperature of about 260° C.,about 1 bar of vacuum, and about 450 rpm. The extrudate was pelletizedand dried at about 100° C. for at least 4 hours. To make test specimens,the dried pellets were injection molded on an Engel ES500/110 HLV110-ton injection molding machine at a nominal barrel temperature of260° C.

The compositions of Table 2 were tested for Chemical Resistance andScratch Resistance. The details of these tests used in the examples areknown to those of ordinary skill in the art, and may be summarized asfollows:

Chemical Resistance is a measure of the percent retention of TensileElongation. Chemical Resistance was evaluated per ISO 4599 usinginjection molded tensile bars (4 mm thick molded tensile bars tested perISO 527) made from the example compositions. The tensile bars areclamped to a semicircular jig to impart a constant applied strain of0.5%. The strained bars are then exposed to a specific chemical for aspecific amount of time, depending on the chemical and desired test.After the exposure, the tensile bars are tested under tensile loadingaccording to ISO 527 (Tensile Elongation at Break was determined using 4mm thick molded tensile bars tested per ISO 527 at a pull rate of 1mm/min. until 1% strain, followed by a rate of 50 mm/min. until thesample broke). The Tensile Elongation to Break of the exposed bars arecompared to the Tensile Elongation to break of the unexposed bars. Theretention of elongation is thus determined; higher retentions ofelongation (as close to 100%) indicate better chemical resistance.

The specific chemicals used in the Chemical Resistance test were: FuelC: 50/50 mixture (by volume) of toluene and isooctane (standard reagentgrade having 99+% purity); Ethyl acetate (standard reagent grade 99+%purity); and Insect repellent: SC Johnson OFF!™ Hyytelö Hyönteissouja(Gel Insect Repellent) from Finland (active ingredients are 200 g/kgN,N-diethyl-m-toluamide and 435 g/kg ethanol).

Scratch Resistance was evaluated per ISO 1518 by dragging a stylus pinon the surface of injection molded plaques made from the examplecompositions at a constant load of 6N. The depth of the scratch producedis measured and reported as the depth in microns. Shallower scratches(lower scratch depths) indicate better scratch resistance.

Melt viscosity (MV) is a measure of a polymer at a given temperature atwhich the molecular chains can move relative to each other. Meltviscosity is dependent on the molecular weight, in that the higher themolecular weight, the greater the entanglements and the greater the meltviscosity, and can therefore be used to determine the extent ofdegradation of the thermoplastic. Degraded materials would generallyshow increased viscosity, and could exhibit reduced physical properties,while lower viscosities show better flow. Melt viscosity is determinedagainst different shear rates, and may be conveniently determined byISO11443. The melt viscosity was measured at 280° C. at a shear rate of10,000s⁻¹.

TABLE 2 C1 C2 C3 C4 Ex. 1 Ex. 2 Ex. 3 Ex. 4 C5 C6 C7 C8 Ex. 5 Ex. 6 Ex.7 Ex. 8 Component Co-PC-1 0 0 0 0 53.54 66.50 0 0 0 0 0 0 49.70 62.95 00 Co-PC-2 0 0 0 0 0 0 53.54 66.50 0 0 0 0 0 0 49.7 62.95 PC-1 40 49.44 00 0 0 0 0 36.73 46.53 0 0 0 0 0 0 PC-2 13.54 17.06 53.54 66.5 0 0 0 012.97 16.42 49.7 62.95 0 0 0 0 ABS 18 13 18 13 18 13 18 13 14 12 14 1214 12 14 12 SAN-1 28 20 28 20 28 20 28 20 0 0 0 0 0 0 0 0 PMMA 0 0 0 0 00 0 0 28 17 28 17 28 17 28 17 PC-Si 0 0 0 0 0 0 0 0 7.5 7.5 7.5 7.5 7.57.5 7.5 7.5 PETS 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.30.3 0.3 AO-1 0.08 0.1 0.08 0.1 0.08 0.1 0.08 0.1 0.4 0.15 0.4 0.15 0.40.15 0.4 0.15 AO-2 0.08 0.1 0.08 0.1 0.08 0.1 0.08 0.1 0.1 0.1 0.1 0.10.1 0.1 0.1 0.1 Chemical Resistance Ethyl Acetate 8 6 10 7 55 52 97 1079 7 11 14 28 90 49 109 2 min Insect 9 5 20 60 99 64 88 89 6 6 7 8 10 1446 71 Repellent Gel 24 hr Fuel C 2 min 0 0 1 1 9 9 18 48 0 0 0 5 16 3532 95 Scratch Resistance 6N Scratch 26 25 26 28 24 21 23 21 23 26 20 2419 21 18 18 Pressure Melt Viscosity 280° C., 10000 33 38 38 44 34 38 3847 46 57 53 70 43 56 49 67 s⁻¹shear rate (Pa-s)

The results of Table 2 show that the samples comprising a polycarbonateterpolymer, an impact modifier, and a rigid copolymer (Ex.1 to Ex.8)have the best chemical and scratch resistance combination. The sampleswhere the rigid copolymer comprises acrylonitrile monomer (Ex.1 to Ex.4) or where the polycarbonate terpolymer comprises more than 50 wt. % ofthe composition and the rigid copolymer comprises (meth)acrylate (Ex. 6and Ex. 8) have the best chemical resistance. The samples having astandard BPA polycarbonate (C1 to C8) instead of the polycarbonateterpolymer generally had very poor chemical resistance. The sampleswhere the rigid copolymer comprises (meth)acrylate (Ex. 5 to Ex. 8) orwhere the polycarbonate terpolymer comprises more than 50 wt. % of thecomposition and the rigid copolymer comprises acrylonitrile monomer (Ex.2 and Ex. 4) had the best scratch resistance.

Additionally, comparing samples C1 to Ex. 1, C2 to Ex. 2, C3 to Ex. 3,C4 to Ex. 4, C5 to Ex. 5, C6 to Ex. 6, C7 to Ex. 7 and C8 to Ex. 8 showsthat by replacing the standard BPA polycarbonate with the polycarbonateterpolymer and keeping the remainder of the composition the same, thechemical resistance increases significantly in all cases, and thescratch resistance improves in all cases.

Additional samples were produced using the materials in Table 1 in theamounts shown below in Table 3. All amounts are parts by weight. SamplesC9 and C10 were produced using commercially available PC/ABS blends, andsamples C11 to C15 were produced by molding 100% of the specified resin(neat, unblended resin). The compositions were molded and tested forchemical and scratch resistance, as detailed above, and the results areshown in Table 3 below.

TABLE 3 C9 C10 C11 C12 C13 C14 C15 Component Co-PC-1 0 0 0 100 0 0 0Co-PC-2 0 0 0 0 100 0 0 PC-1 0 0 0 0 0 0 0 PC-2 0 0 100 0 0 0 0 SAN-1 00 0 0 0 100 0 PMMA 0 0 0 0 0 0 100 Sample 1* 100 0 0 0 0 0 0 Sample 2* 0100 0 0 0 0 0 Chemical Resistance Ethyl Acetate 14 9 8 104 129 0 0 (2min) Insect 14 6 8 4 55 0 0 Repellent Gel (24 hr) Fuel C (2 min) 2 0 152 75 0 0 Scratch Resistance 6N Scratch 27 23 27 18 18 24 23 PressureMelt Viscosity 280° C., 10000 37 45 NT 87 NT NT NT s⁻¹shear rate (Pa-s)*Sample C9 is commercially available Cycoloy ™ C1000HF PC/ABS resin, andSample C10 is commercially available Cycoloy ™ CX1440 PC/ABS resin;NT—Not Tested.

The results in Table 3 show that the polycarbonate terpolymers haveexcellent chemical and scratch resistance, compared to the other neat,unblended and commercially available materials.

Additional samples were produced using the materials in Table 1 in theamounts shown below in Table 4. All amounts are parts by weight. SampleEx. 9 is the same composition as Ex. 8, and Ex. 10 to Ex. 13 are thesame compositions as Ex. 9, with varying amounts of a flow promoteradded. Samples Ex. 14 and Ex. 15 have a blend of a polycarbonate and aterpolymer, and sample Ex. 15 also has the flow promoter added. Thecompositions were molded and tested for chemical resistance and meltviscosity, as detailed above, and the results are shown in Table 4below.

TABLE 4 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Component PC-3 00 0 0 0 20 20 Co-PC-2 62.95 62.95 62.95 62.95 62.95 54.45 54.56 PC-Si7.5 7.5 7.5 7.5 7.5 0 0 ABS 12 12 12 12 12 12 12 SAN-2 0 0 0 0 0 13 13PMMA 17 17 17 17 17 0 0 PETS 0.3 0.3 0.3 0.3 0.3 0.3 0.3 AO-2 0.1 0.10.1 0.1 0.10 0.1 0.1 AO-1 0.15 0.15 0.15 0.15 0.15 0.15 0.15 FP 0 2 4 68 0 5 Pigment 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Chemical ResistanceEthyl Acetate (2 min) 130 120 103 90 117 120 126 Fuel C (2 min) 103 10094 91 90 79 108 Melt Viscosity 280° C., 10000 67 65 62 59 54 70 63s⁻¹shear rate (Pa-s)

The results in Table 4 show that the blends of polycarbonate terpolymer,impact modifier and rigid copolymer have good chemical resistance, andthe addition of the flow promoter improves the flow while maintaining orimproving the chemical resistance of the composition.

While typical embodiments have been set forth for the purpose ofillustration, the foregoing descriptions should not be deemed to be alimitation on the scope herein. Accordingly, various modifications,adaptations, and alternatives may occur to one skilled in the artwithout departing from the spirit and scope herein.

1. A thermoplastic composition comprising: a polycarbonate terpolymercomprising structures derived from at least one of each of structures(I), (II) and (III), wherein (I) is a dihydroxy compound having thestructure (A):

wherein n is 0 to 4 and R^(f) is independently a halogen atom, a C₁₋₁₀hydrocarbon group, or a C₁₋₁₀ halogen substituted hydrocarbon group;(II) comprises a second dihydroxy compound derived from Formula (A) anddifferent from (I) and wherein n and R^(f) are as previously defined;and (III) a third dihydroxy compound not derived from Formula (A),wherein the sum of the mol percent of all of structures (I) and (II) isgreater than 45% relative to the sum of the molar amounts of all ofstructures (I), (II) and (III) in the polycarbonate terpolymer andwherein the polycarbonate terpolymer is amorphous; an impact modifier;and an ungrafted rigid copolymer.
 2. The thermoplastic composition ofclaim 1, comprising: from about 10 to about 85 wt. % of thepolycarbonate terpolymer; from about 5 to about 45 wt. % of the impactmodifier; and from about 10 to about 45 wt. % of the ungrafted rigidcopolymer, wherein the sum of the polycarbonate terpolymer, the impactmodifier and the ungrafted rigid copolymer equals 100 wt. %.
 3. Thethermoplastic composition of claim 1, where the ratio of dihydroxygroups (I):(II):(III) is approximately 1:1:1.
 4. The thermoplasticcomposition of claim 1, wherein the impact modifier is ABS, MBS, ASA,polycarbonate-polysiloxane copolymer, or a combination of two or more ofthe foregoing impact modifiers.
 5. The thermoplastic composition ofclaim 1, wherein the ungrafted rigid copolymer foregoing comprisesacrylonitrile monomer or (meth)acrylate monomer.
 6. The thermoplasticcomposition of claim 5, wherein the ungrafted rigid copolymer is SAN orPMMA.
 7. The thermoplastic composition of claim 1, further comprising aflow promoter.
 8. The thermoplastic composition of claim 7, wherein theflow promoter comprises a low molecular weight hydrocarbon resin derivedfrom petroleum C₅ to C₉ feedstock.
 9. The thermoplastic composition ofclaim 1, wherein in the first dihydroxy (I) of Formula (A) n is
 0. 10.The thermoplastic composition of claim 9, wherein in the seconddihydroxy (II) of Formula (A) n is 1 and R^(f) is C₁.
 11. An articleformed from the thermoplastic composition of claim
 1. 12. Athermoplastic composition comprising a polycarbonate terpolymercomprising structures derived from structures (I), (II) and (III),wherein (I) is a dihydroxy compound having the structure (A):

wherein n is 0 to 4 and R^(f) is independently a halogen atom, a C₁₋₁₀hydrocarbon group, or a C₁₋₁₀ halogen substituted hydrocarbon group;(II) comprises a second dihydroxy compound derived from Formula (A) anddifferent from (I) and wherein n and R^(f) are as previously defined;and (III) a third dihydroxy compound not derived from Formula (A),wherein the sum of the mol percent of all of structures (I) and (II) isgreater than 45% relative to the sum of the molar amounts of all ofstructures (I), (II) and (III) in the polycarbonate terpolymer, theratio of dihydroxy groups (I):(TI):(TTI) is approximately 1:1:1, andwherein the polycarbonate terpolymer is amorphous; an impact modifier;and an ungrafted rigid copolymer.
 13. The thermoplastic composition ofclaim 12, wherein in the first dihydroxy (I) of Formula (A) n is 0 andin the second dihydroxy (II) of Formula (A) n is 1 and R^(f) is C₁. 14.The thermoplastic composition of claim 12, comprising: from about 10 toabout 85 wt. % of the polycarbonate terpolymer; from about 5 to about 45wt. % of the impact modifier; and from about 10 to about 45 wt. % of theungrafted rigid copolymer, wherein the sum of the polycarbonateterpolymer, the impact modifier and the ungrafted rigid copolymer equals100 wt. %.
 15. The thermoplastic composition of claim 12, wherein theungrafted rigid copolymer foregoing comprises acrylonitrile monomer or(meth)acrylate monomer.
 16. The thermoplastic composition of claim 15,wherein the ungrafted rigid copolymer is SAN or PMMA.
 17. Thethermoplastic composition of claim 12, further comprising a flowpromoter comprising a low molecular weight hydrocarbon resin derivedfrom petroleum C₅ to C₉ feedstock.
 18. The thermoplastic composition ofclaim 12, wherein the impact modifier is ABS, MBS, ASA,polycarbonate-polysiloxane copolymer, or a combination of two or more ofthe foregoing impact modifiers.
 19. An article formed from thethermoplastic composition of claim
 12. 20. A thermoplastic compositioncomprising a polycarbonate terpolymer comprising structures derived fromstructures (I), (II) and (III), wherein (I) is a dihydroxy compoundhaving the structure (A):

wherein n is 0; (II) comprises a second dihydroxy compound derived fromFormula (A) wherein n is 1 and R^(f) is C₁; (III) a third dihydroxycompound not derived from Formula (A), wherein the sum of the molpercent of all of structures (I) and (II) is greater than 45% relativeto the sum of the molar amounts of all of structures (I), (II) and (III)in the polycarbonate terpolymer, the ratio of dihydroxy groups(I):(II):(III) is approximately 1:1:1, and wherein the polycarbonateterpolymer is amorphous; an impact modifier; and an ungrafted rigidcopolymer.
 21. The thermoplastic composition of claim 20, wherein thirddihydroxy compound is bisphenol A.